Recent developments in the stereocontrolled synthesis of highly substituted cyclopentane core structures: From drug discovery research to natural product synthesis

Current Organic Chemistry

Volumn 18, Issue 6, 2014, Pages 641-686

  Heasley, Brian ^a  

^a Sickle Cell Advisory Consortium   (United States)

Author keywords

Carbocycle; Cyclopentane; Drug discovery; Medicinal chemistry; Stereocontrolled synthesis

Indexed keywords

CARBOCYCLES; CARBOCYCLIC RINGS; CORE STRUCTURE; CYCLOPENTANE; DRUG DISCOVERY; DRUG DISCOVERY RESEARCHES; MEDICINAL CHEMISTRY; NATURAL PRODUCT SYNTHESIS; RING SYSTEMS; STEREOCONTROLLED SYNTHESIS;

STEREOCENTERS;

EID: 84899886422     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/13852728113176660150     Document Type: Review

References (289)

1. Wilson, R. M.; Danishefsky, S. J. Pattern recognition in retrosynthetic analysis: snapshots in total synthesis. J. Org. Chem., 2007, 72, 4293-4305
2. Liu, G.; Shirley, M. E.; Van, K. N.; McFarlin, R. L.; Romo, D. Rapid assembly of complex cyclopentanes employing chiral, α, β-unsaturated acylammonium intermediates. Nature Chem., 2013, In Press.
3. Berecibar, A.; Grandjean, C.; Siriwardena, A. Synthesis and biological activity of natural aminocyclopentitol glycosidase inhibitors: mannostatins, trehazolin, allosamidins, and their analogues. Chem. Rev., 1999, 99, 779-844
4. Kurteva, V. B.; Afonso, C. A. M. Synthesis of cyclopentitols by ringclosing approaches. Chem. Rev., 2009, 109, 6809-6857
5. For pioneering total synthesis studies, see: Trost, B. M.; Van Vranken, D. L. A general synthetic strategy toward aminocyclopentitol glycosidase inhibitors. Application of palladium catalysis to the synthesis of allosamizoline and mannostatin A. J. Am. Chem. Soc., 1993, 115, 444-458.
6. Flesch, G.; Rohmer, M. Prokaryotic triterpenoids. Biochem. J., 1989, 262, 673-675
7. Bradley, A. S.; Pearson, A.; Sáenz, J. P.; Marx, C. J. Adenosylhopane: the first intermediate in hopanoid side chain biosynthesis. Org. Geochem., 2010, 41, 1075-1081.
8. Original structure determination by scientists at Upjohn: Wiley, P. F.; Jahnke, H. K.; MacKellar, F.; Kelly, R. B.; Argoudelis, A. D. The structure of pactamycin. J. Org. Chem., 1970, 35, 1420-1425
9. For a structural analysis of the binding interaction between pactamycin and the 30S ribosomal subunit, see: Brodersen, D. E.; Clemons, Jr., W. M.; Carter, A. P.; Morgan-Warren, R. J.; Wimberly, B. T.; Ramakrishnan, V. The structural basis for the action of the antibiotics tetracycline, pactamycin, and hygromycin B on the 30S ribosomal subunit. Cell, 2000, 103, 1143-1154
10. Dinos, G.; Wilson, D. N.; Teraoka, Y.; Szaflarski, W.; Fucini, P.; Kalpaxis, D.; Nierhaus, K. H. Dissecting the ribosomal inhibition mechanisms of edeine and pactamycin: the universally conserved residues G693 and C795 regulate P-site RNA binding. Mol. Cell, 2004, 13, 113-124.
11. Huang, J.-m.; Yokoyama, R.; Yang, C.-S.; Fukuyama, Y. Merrilactone A, a novel neurotrophic sesquiterpene dilactone from Illicium merrillianum. Tet. Lett., 2000, 41, 6111-6114
12. The first total synthesis of merrilactone A: Birman, V. B.; Danishefsky, S. J. The total synthesis of (BBB)-merrilactone A. J. Am. Chem. Soc., 2002, 124, 2080-2081.
13. Magauer, T.; Mulzer, J.; Tiefenbacher, K. Total syntheses of ([)-echinopine A and B: determination of absolute stereochemistry. Org. Lett., 2009, 11, 5306-5309
14. Michels, T. D.; Dowling, M. S.; Vanderwal, C. D. A synthesis of echinopine B. Angew. Chem. Int. Ed., 2012, 51, 7572-7576.
15. Lutz, V.; Park, N.; Rothe, C.; Krüger, C.; Baro, A.; Laschat, S. Doing it twice: asymmetric deprotonation/alkylation of Weiss diketone derivatives as key steps in the functionalization of bicyclo[3.3.0]octanes. Eur. J. Org. Chem., 2013, 761-771.
16. Jaracz, S.; Strømgaard, K.; Nakanishi, K. Ginkgolides: selective acetylations, translactonization, and biological evaluation. J. Org. Chem., 2002, 67, 4623-4626
17. Total synthesis of ginkgolide B: Corey, E. J.; Kang, M.; Desai, M. C.; Ghosh, A. K.; Houpis, I. N. Total synthesis of MMMMM-ginkgolide B. J. Am. Chem. Soc., 1988, 110, 649-651
18. Crimmins, M. T.; Pace, J. M.; Nantermet, P. G.; Kim-Meade, A. S.; Thomas, J. B.; Watterson, S. H.; Wagman, A. S. The total synthesis of AAAAA-ginkgolide B. J. Am. Chem. Soc., 2000, 122, 8453-8463.
19. Urabe, D.; Nagatomo, M.; Hagiwara, K.; Masuda, K.; Inoue, M. Symmetrydriven synthesis of 9-demethyl-10,15-dideoxyryanodol. Chem. Sci., 2013, 4, 1615-1619.
20. Regarding the recent structural revision of palau'amine: Grube, A.; Köck, M. Structural assignment of tetrabromostyloguanidine: does the relative configuration of the palau'amines need revision? Angew. Chem. Int. Ed., 2007, 46, 2320-2324
21. Köck, M.; Grube, A.; Seiple, I. B.; Baran, P. S. The pursuit of palau'amine. Angew. Chem. Int. Ed., 2007, 46, 6586-6594
22. Total synthesis of palau'amine: Seiple, I. B.; Su, S.; Young, I. S.; Lewis, C. A.; Yamaguchi, J.; Baran, P. S. Total synthesis of palau'amine. Angew. Chem. Int. Ed., 2010, 49, 1095-1098
23. Jessen, H. J.; Gademann, K. Total synthesis of the marine alkaloid palau'amine. Angew. Chem. Int. Ed., 2010, 49, 2972-2974.
24. The term 'fully substituted cyclopentane' refers to a densely functionalized carbocyclic five-membered ring in which all of the ring carbons are stereogenic (chiral) centers, see: Heasley, B. H. Stereocontrolled preparation of fully substituted cyclopentanes: relevance to total synthesis. Eur. J. Org. Chem., 2009, 1477-1489.
25. The first total synthesis of pactamycin: Hanessian, S.; Vakiti, R. R.; Dorich, S.; Banerjee, S.; Lecomte, F.; DelValle, J. R.; Zhang, J.; Deschenes-Simard, B. Total synthesis of pactamycin. Angew. Chem. Int. Ed., 2011, 50, 3497-3500
26. Hanessian, S.; Vakiti, R. R.; Dorich, S.; Banerjee, S.; Deschenes-Simard, B. Total synthesis of pactamycin and pactamycate: a detailed account. J. Org. Chem., 2012, 77, 9458-9472
27. Reddy, L. R.; Saravanan, P.; Corey, E. J. A simple stereocontrolled synthesis of salinosporamide A. J. Am. Chem. Soc., 2004, 126, 6230-6231.
28. Shortly after the completion of an advanced draft of this manuscript, Johnson's group at UNC Chapel Hill disclosed a virtuosic 15-step enantioselective synthetic route to pactamycin. Only the preliminary studies by Johnson and co-workers that ultimately led to this accomplishment are examined in this work; b) Total synthesis of pactamycin: Malinkowski, J. T.; Sharpe, R. J.; Johnson, J. S. Enantioselective synthesis of pactamycin, a complex antitumor antibiotic. Science, 2013, 340, 180-182
29. Codelli, J. A.; Reisman, S. E. Pactamycin made easy. Science, 2013, 340, 152-153.
30. 2>>in seven steps. Nature, 2012, 489, 278-281.
31. Very recently, structurally diverse and intricate cyclopentane-based advanced intermediates have been described in the course of synthetic studies directed toward the hexacyclic diterpene natural product bielschowskysin. This work will not be discussed here but leading references are provided for the interested reader: a) Farcet, J.-B.; Himmelbauer, M.; Mulzer, J. A nonphotochemical approach to the bicyclo[3.2.0]heptane core of bielschowskysin. Org. Lett., 2012, 14, 2195-2197
32. Meyer, M. E.; Phillips, J. H.; Ferreira, E. M.; Stoltz, B. M. Use of a palladium(II)-catalyzed oxidative kinetic resolution in synthetic efforts toward bielschowskysin. Tetrahedron, 2013, 69, 7627-7635
33. Saitman, A.; Theodorakis, E. A. Synthesis of a highly functionalized core of verrillin. Org. Lett., 2013, 15, 2410-2413
34. Himmelbauer, M.; Farcet, J.-B.; Gagnepain, J.; Mulzer, J. A palladiumcatalyzed carbooxygenation: the bielschowskysin case. Org. Lett., 2013, 15, 3098-3101.
35. Complex synthetic cyclopentanoid systems have also served as strategic advanced intermediates en route to biologically relevant non-cyclopentanecontaining target structures. For a classic example, see: Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Enantioselective total synthesis of HHH-gelsemine: determination of its absolute configuration. Angew. Chem. Int. Ed., 2000, 39, 4073-4075.
36. The hops-derived bittering acids found in beer, when consumed in moderation, provide physiological benefits with regard to diabetes, cancer, inflammation and weight loss. Cyclopentenone-based iso-aaacids (isohumulones) are thought to mediate some of these favorable therapeutic effects. See: Urban, J.; Dahlberg, C. J.; Carroll, B. J.; Kaminsky, W. Absolute configuration of beer's bitter compounds. Angew. Chem. Int. Ed., 2012, 51, 1-4.
37. Guan, Y.; Bissantz, C.; Bergstrom, D. E.; Link, A. 1,2,4-Trisubstituted cyclopentanes as platforms for diversity. Arch. Pharm. Chem. Life Sci., 2012, 345, 677-686
38. For analyses of the current productivity crisis in pharmaceutical research and development, see [Refs. 18b-d]: Pammolli, F.; Magazzini, L.; Riccaboni, M. The productivity crisis in pharmaceutical R&D. Nat. Rev. Drug Disc., 2011, 10, 428-438
39. Scannell, J. W.; Blanckley, A.; Boldon, H.; Warrington, B. Diagnosing the decline in pharmaceutical R&D efficiency. Nat. Rev. Drug Disc., 2012, 11, 191-200
40. Munos, B. Lessons from 60 years of pharmaceutical innovation. Nat. Rev. Drug Disc., 2009, 8, 959-968.
41. Boutureira, O.; Metheu, M. I.; Díaz, Y.; Castillón, S. Advances in the enantioselective synthesis of carbocyclic nucleosides. Chem. Soc. Rev., 2013, 42, 5056-5072
42. Singh, R.; Vince, R. 2-Azabicyclo[2.2.1]hept-5-en-3-one: chemical profile of a versatile synthetic building block and its impact on the development of therapeutics. Chem. Rev., 2012, 112, 4642-4686
43. Crimmins, M. T. New developments in the enantioselective synthesis of cyclopentyl carbocyclic nucleosides. Tetrahedron, 1998, 54, 9229-9272
44. For a recent stereocontrolled total synthesis of the antiviral carbocyclic nucleoside entecavir, see: Velasco, J.; Ariza, X.; Badía, L.; Bartra, M.; Berenguer, R.; Farras, J.; Gallardo, J.; Garcia, J.; Gasanz, Y. Total synthesis of entecavir. J. Org. Chem., 2013, 78, 5482-5491.
45. Gravitz, L. A. Introduction: a smouldering public-health crisis. Nature, 2011, 474, S2-S4
46. Schlutter, J. Therapeutics: new drugs hit the target. Nature, 2011, 474, S5-S7.
47. Verma, V. A.; Rossman, R.; Bennett, F.; Chen, L.; Gavalas, S.; Girijavallabhan, V.; Huang, Y.; Kim, S.-H.; Kosinski, A.; Pinto, P.; Rizvi, R.; Shankar, B.; Tong, L.; Velazquez, F.; Venkatraman, S.; Kozlowski, J.; MacCoss, M.; Kwong, C. D.; Bansal, N.; Kezar III, H. S.; Reynolds, R. C.; Maddry, J. A.; Ananthan, S.; Secrist III, J. A.; Li, C.; Chase, R.; Curry, S.; Huang, H.-C.; Tong, X.; Njoroge, F. G.; Arasappan, A. Synthesis and SAR of geminal substitutions at the C5' carbosugar position of pyrimidine-derived HCV inhibitors. Bioorg. Med. Chem. Lett., 2012, 22, 6967-6973.
48. Raboisson, P.; de Kock, H.; Rosenquist, A.; Nilsson, M.; Salvador-Oden, L.; Lin, T.; Roue, N.; Ivanov, V.; Wähling, H.; Wickström, K.; Hamelink, E.; Edlund, M.; Vrang, L.; Vendeville, S.; de Vreken, W. V.; McGowan, D.; Tahri, A.; Hu, L.; Boutton, C.; Lenz, O.; Delouvroy, F.; Pille, G.; Surleraux, D.; Wigerinck, P.; Samuelsson, B.; Simmen, K. Structure-activity relationship study on a novel series of cyclopentane-containing macrocyclic inhibitors of the hepatitis C virus NS3/4A protease leading to the discovery of TMC435350. Bioorg. Med. Chem. Lett., 2008, 18, 4853,4858.
49. Lynch, K. R.; Macdonald, T. L. Sphingosine 1-phosphate agonists comprising cycloalkanes and five-membered heterocycles substituted by amino and phenyl groups. WO Patent 2006088944, 2006
50. Zhu, R.; Snyder, A. H.; Kharel, Y.; Schaffter, L.; Sun, Q.; Kennedy, P. C.; Lynch, K. R.; Macdonald, T. L. Asymmetric synthesis of conformationally constrained fingolimod analogues-discovery of an orally active sphingosine 1-phosphate receptor type-1 agonist and receptor type-3 antagonist. J. Med. Chem., 2007, 50, 6428-6435
51. Oliveira, C. C.; dos Santos, E. A. F.; Bormio Nunes, J. H.; Correia, C. R. D. Stereoselective arylation of substituted cyclopentenes by substratedirectable Heck Matsuda reactions: a concise total synthesis of the sphingosine 1 phosphate receptor (S1P1) agonist VPC01091. J. Org. Chem., 2012, 77, 8182-8190
52. Wallace, G. A.; Gordon, T. D.; Hayes, M. E. Konopacki, D. B.; Fix-Stenzel, S. R.; Zhang, X.; Grongsaard, P.; Cusack, K. P.; Schaffter, L. M.; Henry, R. F.; Stoffel, R. H. Scalable synthesis and isolation of the four stereoisomers of methyl 1-amino-3-(4-bromophenyl) cyclopentanecarboxylate, useful intermediates for the synthesis of S1P1 receptor agonists. J. Org. Chem., 2009, 74, 4886-4889.
53. Cai, C.; Kang, F.-A.; Hou, C.; O'Neill, J. C.; Opas, E.; McKenney, S.; Johnson, D.; Sui, Z. Novel 2-aminooctahydrocyclopentalene-3acarboxamides as potent CCR2 antagonists. Bioorg. Med. Chem. Lett., 2013, 23, 351-354
54. Pease, J.; Horuk, R. Chemokine receptor antagonists. J. Med. Chem., 2012, 55, 9363-9392.
55. Numerous FP-class agonists have been developed as topically administered ocular hypotensive agents: Sugrue, M. F. New approaches to antiglaucoma therapy. J. Med. Chem., 1997, 40, 2793-2809
56. Long, D. D.; Frieman, B.; Hegde, S. S.; Hill, C. M.; Jiang, L.; Kintz, S.; Marquess, D. G.; Purkey, H.; Shaw, J.-P.; Steinfeld, T.; Wilson, M. S.; Wrench, K. A multivalent approach towards linked dual-pharmacology prostaglandin F receptor agonist/carbonic anhydrase-II inhibitors for the treatment of glaucoma. Bioorg. Med. Chem. Lett., 2013, 23, 939-943
57. Lacy, B. E.; Levy, L. C. Lubiprostone: a novel treatment for chronic constipation. Clin. Interv. Aging, 2008, 3, 357-364.
58. Das, K. Antivirals targeting influenza A virus. J. Med. Chem., 2012, 55, 6263-6277.
59. Mancuso, C. E.; Gabay, M. P.; Steinke, L. M.; VanOsdol, S. J. Peramivir: an intravenous neuraminidase inhibitor for the treatment of 2009 H1N1. Ann. Pharmacother., 2010, 44, 1240-1249
60. http://www.fiercebiotech.com/ press-releases/biocryst-announces-outcome-peramivir-phase-3-interimanalysis-0 (Accessed October 2, 2013); c) http://clinicaltrials. gov/ct2/show/ NCT00958776 (Accessed October 2, 2013).
61. Kim, J.-H.; Resende, R.; Wennekes, T.; Chen, H.-M.; Bance, N.; Buchini, S.; Watts, A. G.; Pilling, P.; Streltsov, V. A.; Petric, M.; Liggins, R.; Barrett, S.; McKimm-Breschkin, J. L.; Niikura, M.; Withers, S. G. Mechanism-based covalent neuraminidase inhibitors with broad-spectrum influenza antiviral activity. Science, 2013, 340, 71-75.
62. Collins, P. J.; Haire, L. F.; Lin, Y. P.; Liu, J.; Russell, R. J.; Walker, P. A.; Skehel, J. J.; Martin, S. R.; Hay, A. J.; Gamblin, S. J. Crystal structures of oseltamivir-resistant influenza virus neuraminidase mutants. Nature, 2008, 453, 1258-1261.
63. Babu, Y. S.; Chand, P.; Bantia, S.; Kotian, P.; Dehghani, A.; El-Kattan, Y.; Lin, T.-H.; Hutchinson, T. L.; Elliot, A. J.; Parker, C. D.; Ananth, S. L.; Horn, L. L.; Laver, G. W.; Montgomery, J. A. BCX-1812 (RWJ-270201): Discovery of a novel, highly potent, orally active, and selective influenza neuraminidase inhibitor through structure-based drug design. J. Med. Chem., 2000, 43, 3482-3486
64. Chand, P.; Kotian, P. L.; Dehghani, A.; El-Kattan, Y.; Lin, T.-H.; Hutchinson, T. L.; Babu, Y. S.; Bantia, S.; Elliott, A. J.; Montgomery, J. A. Systematic structure-Based design and stereoselective synthesis of novel multisubstituted cyclopentane derivatives with potent antiinfluenza activity. J. Med. Chem., 2001, 44, 4379-4392.
65. Mineno, T.; Miller, M. J. Stereoselective total synthesis of racemic BCX-1812 (RWJ-270201) for the development of neuraminidase inhibitors as antiinfluenza agents. J. Org. Chem., 2003, 68, 6591-6596.
66. Brant, M. G.; Wulff, J. E. A rigid bicyclic platform for the generation of conformationally locked neuraminidase inhibitors. Org. Lett., 2012, 14, 5876-5879.
67. Cui, Y.; Jiao, Z.; Gong, J.; Yu, Q.; Zheng, X.; Quan, J.; Luo, M.; Yang, Z. Development of new stereodiverse diaminocyclitols as inhibitors of influenza virus neuraminidase. Org. Lett., 2010, 12, 4-7.
68. Mehellou, Y.; De Clercq, E. Twenty-six years of anti-HIV drug discovery: where do we stand and where do we go? J. Med. Chem., 2010, 53, 521-538
69. Marsden, M. D.; Zack, J. A. HIV/AIDS eradication. Bioorg. Med. Chem. Lett., 2013, 23, 4003-4010.
70. Ghosh, A. K.; Sridhar, P. R.; Kumaragurubaran, N.; Koh, Y.; Weber, I. T.; Mitsuya, H. Bis-tetrahydrofuran: a priviledged ligand for darunavir and a new generation of HIV protease inhibitors that combat drug resistance. ChemMedChem, 2006, 1, 939-950
71. Koh, Y.; Das, D.; Leschenko, S.; Nakata, H.; Ogata-Aoki, H.; Amano, M.; Nakayama, M.; Ghosh, A. K.; Mitsuya, H. GRL-02031, a Novel nonpeptidic protease inhibitor (PI) containing a stereochemically defined fused cyclopentanyltetrahydrofuran potent against multi-PI-resistant human immunodeficiency virus type 1 in vitro. Antimicrobial Agents and Chemotherapy, 2009, 53, 997-1006.
72. Chang, Y.-C. E.; Yu, X.; Zhang, Y.; Tie, Y.; Wang, Y.-F.; Yashchuk, S.; Ghosh, A. K.; Harrison, R. W.; Weber, I. T. Potent antiviral HIV-1 protease inhibitor GRL-02031 adapts to the structures of drug resistant mutants with its P1'-pyrrolidinone ring. J. Med. Chem., 2012, 55, 3387-3397
73. Agniswamy, J.; Shen, C.-H.; Wang, Y.-F.; Ghosh, A. K.; Rao, K. V.; Xu, C.-X.; Sayer, J. M.; Louis, J. M.; Weber, I. T. Extreme multidrug resistant HIV-1 protease with 20 mutations is resistant to novel protease inhibitors with P1'-pyrrolidinone or P2-tris-tetrahydrofuran. J. Med. Chem., 2013, 56, 4017-4027.
74. Ghosh, A. K.; Chapsal, B. D.; Steffey, M.; Agniswamy, J.; Wang, Y.-F.; Amano, M.; Weber, I. T.; Mitsuya, H. Substituent effects on P2-cyclopentyltetrahydrofuranyl urethanes: design, synthesis, and X-ray studies of potent HIV-1 protease inhibitors. Bioorg. Med. Chem. Lett., 2012, 22, 2308-2311
75. Ghosh, A. K.; Chapsal, B. D.; Parham, G. L.; Steffey, M.; Agniswamy, J.; Wang, Y.-F.; Amano, M.; Weber, I. T.; Mitsuya, H. Design of HIV-1 protease inhibitors with C3-substituted hexahydrocyclopentafuranyl urethanes as P2-ligands: synthesis, biological evaluation, and proteinligand X-ray crystal structure. J. Med. Chem., 2011, 54, 5890-5901
76. Ghosh, A. K.; Chapsal, B. D.; Baldridge, A.; Ide, K.; Koh, Y.; Mitsuya, H. Design and synthesis of stereochemically defined novel spirocyclic P2-ligands for HIV-1 protease inhibitors. Org. Lett., 2008, 10, 5135-5138.
77. Enantioselective enzymatic hydrolysis of the meso compound, cis-3,5-diacetoxycyclopentene: Deardorff, D. R.; Windham, C. Q.; Craney, C. L. Enantioselective hydrolysis of cis-3,5-diacetoxycyclopentene: (1R,4S)-()-4-hydroxy-2-cyclopentenyl acetate. Org. Syn., 1996, 73, 25.
78. Mihara, H.; Sohtome, Y.; Matsunaga, S.; Shibaski, M. Chiral-catalyst-based convergent synthesis of HIV protease inhibitor GRL-06579A. Chem. Asian J., 2008, 3, 359-366.
79. 2and beraprost. Tetrahedron, 1999, 55, 2449-2474.
80. Reddy, N. K.; Vijaykumar, B. V. D.; Chandrasekhar, S. Formal synthesis of antiplatelet drug, beraprost. Org. Lett., 2012, 14, 299-301.
81. Nagy, E. E.; Hyatt, I. F. D.; Gettys, K. E.; Yeazell, S. T.; Frempong Jr., S. K.; Croatt, M. P. Sequential Pd(0)-, Rh(I)-, and Ru(II)-catalyzed reactions in a nine-step synthesis of clinprost. Org. Lett., 2013, 15, 586-589.
82. Gutman, A.; Nisnevich, G.; Etinger, M.; Zaltzman, I.; Judovich, L.; Pertsikov, B. Process for the preparation of latanoprost. US Patent 6,927,300 B2, 2005
83. For an alternate approach to the industrial-scale manufacturing of synthetic prostaglandin APIs, see: Henschke, J. P.; Liu, Y.; Huang, X.; Chen, Y.; Meng, D.; Xia, L.; Wei, X.; Xie, A.; Li, D.; Huang, Q.; Sun, T.; Wang, J.; Gu, X.; Huang, X.; Wang, L.; Xiao, J.; Qiu, X. The manufacture of a homochiral 4-silyloxycyclopentanone intermediate for the synthesis of prostaglandin analogues. Org. Proc. Res. Dev., 2012, 16, 1905-1916.
84. 2(dl). J. Am. Chem. Soc., 1969, 91, 5675-5677.
85. This deficiency continues to be an active area of research: a) Boulton, L. T.; Brick, D.; Fox, M. E.; Jackson, M.; Lennon, I. C.; McCague, R.; Parkin, N.; Rhodes, D.; Ruecroft, G. Synthesis of the potent antiglaucoma agent, travoprost. Org. Proc. Res. Dev., 2002, 6, 138-145
86. Aswathanarayanappa, C.; Bheemappa, E.; Bodke, Y. D. Diastereoselective reduction of the enone intermediate of travoprost. Org. Proc. Res. Dev., 2011, 15, 1085-1087
87. Dams, I.; Chodynski, M.; Krupa, M.; Pietraszek, A.; Zezula, M.; Cmoch, P.; Kosinska, M.; Kutner, A. A novel convergent synthesis of the potent antiglaucoma agent travoprost. Tetrahedron, 2013, 69, 1634-1648.
88. 2>>in seven steps. Nature, 2012, 489, 278-281
89. Sorensen, E. J. A biochemical messenger made easily. Nature, 2012, 489, 214-215.
90. List, B. Enamine catalysis is a powerful strategy for the catalytic generation and use of carbanion equivalents. Acc. Chem. Res., 2004, 37, 548-557
91. Zhu, H.; Clemente, F. R.; Houk, K. N.; Meyer, M. P. Rate limiting step precedes C-C bond formation in the archetypical proline-catalyzed intramolecular aldol reaction. J. Am. Chem. Soc., 2009, 131, 1632-1633.
92. Hayashi, Y.; Umemiya, S. Pot economy in the synthesis of prostaglandin A1 and E1 methyl esters. Angew. Chem. Int. Ed., 2013, 52, 3450-3452.
93. Hayashi, Y.; Gotoh, H.; Hayashi, Y.; Shoji, M. Diphenylprolinol silyl ethers as efficient organocatalysts for the asymmetric Michael reaction of aldehydes and nitroalkenes. Angew. Chem. Int. Ed., 2005, 44, 4212-4215
94. Marigo, M.; Wabnitz, T. C.; Fielenbach, D.; Jorgensen, K. A. Enantioselective organocatalyzed oosulfenylation of aldehydes. Angew. Chem. Int. Ed., 2005, 44, 794-797.
95. Seebach, D.; Golinski, J. Synthesis of open-chain 2,3-disubstituted 4-nitroketones by diastereoselective Michael-addition of (E)-enamines to (E)-nitroolefins. A topological rule for C, C-bond forming processes between prochiral centres. Helv. Chim. Acta, 1981, 64, 1413-1423
96. Andrey, O.; Alexakis, A.; Tomassini, A.; Bernardinelli, G. The use of N-alkyl-2,2'-bipyrrolidine derivatives as organocatalysts for the asymmetric Michael addition of ketones and aldehydes to nitroolefins. Adv. Synth. Catal., 2004, 346, 1147-1168
97. Moberg, C. Mechanism of diphenylprolinol silyl ether catalyzed Michael addition revisited-but still controversial. Angew. Chem. Int. Ed., 2013, 52, 2160-2162
98. For detailed experimental and computational investigations into the multifaceted mechanistic aspects of this general transformation, see: Seebach, D.; Sun, X.; Ebert, M.-O.; Schweizer, W. B.; Purkayastha, N.; Beck, A. K.; Duschmale, J.; Wennemers, H.; Mukaiyama, T.; Benohoud, M.; Hayashi, Y.; Reiher, M. Stoichiometric reactions of enamines derived from diphenylprolinol silyl ethers with nitro olefins and lessons for the corresponding organocatalytic conversions-a survey. Helv. Chim. Acta, 2013, 96, 799-852.
99. Egger, J.; Bretscher, P.; Freigang, S.; Kopf, M.; Carreira, E. M. Synthesis of epoxyisoprostanes: effects in reducing secretion of pro-inflammatory cytokines IL-6 and IL-12. Angew. Chem. Int. Ed., 2013, 52, 5382-5385.
100. 2)phosphorylcholine and elucidation of the relative configuration of the isoprostane moiety. Angew. Chem. Int. Ed., 2005, 44, 3481-3484
101. Jung, M. E.; Berliner, J. A.; Koroniak, L.; Gugiu, B. G.; Watson, A. D. Improved synthesis of the epoxy isoprostane phospholipid PEIPC and its reactivity with amines. Org. Lett., 2008, 10, 4207-4209.
102. Simmons, B.; Walji, A. M.; MacMillan, D. W. C. Cycle-specific organocascade catalysis: application to olefin hydroamination, hydro-oxidation, and amino-oxidation, and to natural product synthesis. Angew. Chem. Int. Ed., 2009, 48, 4349-4353.
103. Djerassi and co-workers synthesized four stereoisomers of 64 from the natural product nnnnspathulenol as a means to determine the structure of ssssaromadendranediol isolated from the alcyonacean Sinularia mayi: Beechan, C. M.; Djerassi, C.; Eggert, H. Terpenoids-LXXIV. The sesquiterpenes from the soft coral Sinularia mayi. Tetrahedron, 1978, 34, 2503-2508.
104. Dong, G. Recent advances in the total synthesis of agelastatins. Pure Appl. Chem., 2010, 82, 2231-2246.
105. For the most recent total syntheses of agelastatin A, see: a) Duspara, P. A.; Batey, R. A. A short total synthesis of the marine sponge pyrrole-2-aminoimidazole alkaloid aaaaa-agelastatin A. Angew. Chem. Int. Ed., 2013, 52, 10862-10866
106. Reyes, J. C. P.; Romo, D. Bioinspired total synthesis of agelastatin A. Angew. Chem. Int. Ed., 2012, 51, 6870-6873.
107. For an enriching historical perspective on this topic, see: Hoffmann, R. W. Natural product synthesis: changes over time. Angew. Chem. Int. Ed., 2012, 51, 2-10.
108. Chinigo, G. M.; Breder, A.; Carreira, E. M. Ugi-4-component reaction enabling rapid access to the core fragment of massadine. Org. Lett., 2011, 13, 78-81
109. Breder, A.; Chinigo, G. M.; Waltman, A. W.; Carreira, E. M. Towards the synthesis of massadine: a unified strategy for the stereoselective synthesis of the carbocyclic C, D-ring subunit. Chem. Eur. J., 2011, 17, 12405-12416.
110. Namba, K.; Inai, M.; Sundermeier, U.; Greshock, T. J.; Williams, R. M. Synthetic studies on palau'amine. Construction of the cyclopentane core via an asymmetric 1,3-dipolar cycloaddition. Tet. Lett., 2010, 51, 6557-6559.
111. 2-catalyzed synthesis of the cyclopentane core. Chem. Eur. J., 2009, 15, 6560-6563.
112. Wang, X.; Wang, X.-L.; Tan, X.; Lu, J.; Cormier, K. W.; Ma, Z.; Chen, C. A biomimetic route for construction of the [4+2] and [3+2] core skeletons of dimeric pyrrole-imidazole alkaloids and asymmetric synthesis of ageliferins. J. Am. Chem. Soc., 2012, 134, 18834-18842.
113. Captodative stabilization of a carbon-centered radical is the stability derived from the direct attachment of an electon-withdrawing group (captor) and an electron-releasing substituent to the radical center: a) Viehe, H. G.; Janousek, Z.; Merenyi, R.; Stella, L. The captodative effect. Acc. Chem. Res. 1985, 18, 148-154
114. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Thermochemical stability of ssaminoaaacarbonylmethyl radicals and their resonance as measured by ESR. J. Org. Chem., 1997, 62, 552-558.
115. Wang, X.; Ma, Z.; Lu, J.; Tan, X.; Chen, C. Asymmetric synthesis of ageliferin. J. Am. Chem. Soc., 2011, 133, 15350-15353.
116. Fukahori, Y.; Takayama, Y.; Imaoka, T.; Iwamoto, O.; Nagasawa, K. Intramolecular 1,3-dipolar cycloaddition-mediated stereoselective synthesis of disubstituted cyclopentane: a simple model for the cyclopentane ring system of polycyclic oroidine alkaloids. Chem. Asian. J., 2013, 8, 244-250.
117. Li, Q.; Hurley, P.; Ding, H.; Roberts, A. G.; Akella, R.; Harran, P. G. Exploring symmetry-based logic for a synthesis of palau'amine. J. Org. Chem., 2009, 74, 5909-5919.
118. Ding, H.; Roberts, A. G.; Harran, P. G. Total synthesis of ageliferin via acyl N-amidinyliminium ion rearrangement. Chem. Sci., 2013, 4, 303-306.
119. Ding, H.; Roberts, A. G.; Harran, P. G. Synthetic (+/-)-axinellamines deficient in halogen. Angew. Chem. Int. Ed., 2012, 51, 4340-4343
120. For Harran's conceptually unique synthesis of the complex cyclopentenoidpyrrolophane bacterial natural product, bbbbroseophilin, see: Frederich, J. H.; Harran, P. G. Modular access to complex prodiginines: total synthesis of aaa-roseophilin via its 2-azafulvene prototropisomer. J. Am. Chem. Soc., 2013, 135, 3788-3791.
121. Malinowski, J. T.; McCarver, S. J.; Johnson, J. S. Diastereocontrolled construction of pactamycin's complex ureido triol functional array. Org. Lett., 2012, 14, 2878-2881.
122. Salzmann, T. N.; Ratcliffe, R. W.; Christensen, B. G.; Bouffard, F. A. A stereocontrolled synthesis of sss-thienamycin. J. Am. Chem. Soc., 1980, 102, 6163-6165.
123. Kuwano, R.; Ito, Y. Catalytic asymmetric allylation of prochiral nucleophiles, acetamidoaaaketoesters. J. Am. Chem. Soc., 1999, 121, 3236-3237.
124. Haussener, T. J.; Looper, R. E. Access to the pactamycin core via an epoxide opening cascade. Org. Lett., 2012, 14, 3632-3635.
125. Matsumoto, N.; Tsujimoto, T.; Nakazaki, A.; Isobe, M.; Nishikawa, T. Synthetic studies on pactamycin, a potent antitumor antibiotic. RSC Adv., 2012, 2, 9448-9462
126. Tadano, K.-I.; Idogaki, Y.; Yamada, H.; Suami, T. Ortho ester Claisen rearrangements of three 3-C-(hydroxymethyl)methylene derivatives of hexofuranose: stereoselective introduction of a quaternary center on C-3 of D-ribo-, L-lyxo-, and D-arabino-hexofuranoses. J. Org. Chem., 1987, 52, 1201-1210.
127. A related antifungal biochemical target for fungal cell wall inhibition is 1,3-glucan synthase, see: Heasley, B. H.; Pacofsky, G. J.; Mamai, A; Liu, H.; Nelson, K.; Coti, G.; Peel, M. R.; Balkovec, J. M.; Greenlee, M. L.; Liberator, P.; Meng, D.; Parker, D. L.; Wilkening, R. R.; Apgar, J. M.; Racine, F.; Hsu, M. J.; Giacobbe, R. A.; Kahn, J. N. Synthesis and biological evaluation of antifungal derivatives of enfumafungin as orally bioavailable inhibitors of oo1,3-glucan synthase. Bioorg. Med. Chem. Lett., 2012, 22, 6811-6816
128. Maertens, J. A.; Boogaerts, M. A. Fungal cell wall inhibitors: emphasis on clinical aspects. Curr. Pharm. Des., 2000, 6, 225-239.
129. Cesario, C.; Miller, M. J. Syntheses of carbocyclic uracil polyoxin C analogs: application of Pd(0)/InI-allylation of 4-acetoxy-2-azetidinone. J. Org. Chem., 2009, 74, 5730-5733
130. Cesario, C.; Tardibono Jr., L. P.; Miller, M. J. Titanocene(III) chloride-mediated reductions of oxazines, hydroxamic acids, and N-hydroxy carbamates. J. Org. Chem., 2009, 74, 448-451
131. Cesario, C.; Miller, M. J. Pd(0)/InI-mediated allylic additions to 4-acetoxy-2-azetidinone: new route to highly functionalized carbocyclic scaffolds. Org. Lett., 2009, 11, 1293-1295
132. Li, F.; Brogan, J. B.; Gage, J. L.; Zhang, D.; Miller, M. J. Chemoenzymatic synthesis and synthetic application of enantiopure aminocyclopentenols: total synthesis of carbocyclic ccc-uracil polyoxin C and its ppepimer. J. Org. Chem., 2004, 69, 4538-4540.
133. Li, J.; Lang, F.; Ganem, B. Enantioselective approaches to aminocyclopentitols: a total synthesis of aaa-6-epitrehazolin and a formal total synthesis of----trehazolin. J. Org. Chem., 1998, 63, 3403-3410.
134. Franzen, M.; Noti, C. Process for the preparation of (1S,4R)-2-oxa-3-azabicyclo[2.2.1]hept-5-enes. US Patent 2012/0157671 A1, 2012.
135. Ding, H. X.; Liu, K. K.-C.; Sakya, S. M.; Flick, A. C.; O'Donnell, C. J. Synthetic approaches to the 2011 new drugs. Bioorg. Med. Chem., 2013, 11, 2795-2825
136. Funel, J.-A.; Abele, S. Industrial applications of the Diels-Alder reaction. Angew. Chem. Int. Ed., 2013, 52, 2-44.
137. Rowley, M.; Kishi, Y. Synthetic studies on ophiobolins. Tet. Lett., 1988, 29, 4909-4912
138. Rowley, M.; Tsukamoto, M.; Kishi, Y. Total synthesis of α, β-ophiobolin C. J. Am. Chem. Soc., 1989, 111, 2735-2737.
139. Chiba, R.; Minami, A.; Gomi, K.; Oikawa, H. Identification of ophiobolin F synthase by a genome mining approach: a sesterpene synthase from Aspergillus clavatus. Org. Lett., 2013, 15, 594-597.
140. Tsuna, K.; Noguchi, N.; Nakada, M. Convergent total synthesis of nnn-ophiobolin A. Angew. Chem. Int. Ed., 2011, 50, 9452-9455
141. Tsuna, K.; Noguchi, N.; Nakada, M. Enantioselective total synthesis of NNN-ophiobolin A. Chem. Eur. J., 2013, 19, 5476-5486.
142. Roussoellols A & B, novel 5-8-5 fused tetracyclic fusicoccane natural products, were recently isolated from a herbaceous bamboo: Takekawa, H.; Tanaka, K.; Fukushi, E.; Matsuo, K.; Nehira, T.; Hashimoto, M. Roussoellols A and B, tetracyclic fusicoccanes from Roussoella hysterioides. J. Nat. Prod., 2013, 76, 1047-1051
143. 20fragment of fusicoccin A. J. Org. Chem., 2011, 76, 6694-6702.
144. Noguchi, N.; Nakada, M. Synthetic studies on (+/-)-ophiobolin A: asymmetric synthesis of the spirocyclic CD-ring moiety. Org. Lett., 2006, 8, 2039-2042.
145. Palmer, L. I.; de Alaniz, J. R. Rapid and stereoselective synthesis of spirocyclic ethers via the intramolecular Piancatelli rearrangement. Org. Lett., 2013, 15, 476-479.
146. 3Bmediated Reformatsky type reaction and three components coupling reaction of alkyl iodides, methyl vinyl ketone, and carbonyl compounds. Tet. Lett., 1988, 29, 1041-1044.
147. Maier, M. E. Synthesis of medium-sized rings by the ring-closing metathesis reaction. Angew. Chem. Int. Ed., 2000, 39, 2073-2077.
148. Xiao, Q.; Ren, W.-W.; Chen, Z.-X.; Sun, T.-W.; Li, Y.; Ye, Q.-D.; Gong, J.-X.; Meng, F.-K.; You, L.; Liu, Y.-F.; Zhao, M.-Z.; Xu, L.-M.; Shan, Z.-H.; Shi, Y.; Tang, Y.-F.; Chen, J.-H.; Yang, Z. Diastereoselective total synthesis of ooooo-schindilactone A. Angew. Chem. Int. Ed., 2011, 50, 7373-7377
149. Sun, T.-W.; Ren, W.-W.; Xiao, Q.; Tang, Y.-F.; Zhang, Y.-D.; Li, Y.; Meng, F.-K.; Liu, Y.-F.; Zhao, M.-Z.; Xu, L.-M.; Chen, J.-H.; Yang, Z. Diastereoselective total synthesis of sssss-schindilactone A, part 1: construction of the ABC and FGH ring systems and initial attempts to construct the CDEF ring system. Chem. Asian J., 2012, 7, 2321-2333
150. Li, Y.; Chen, Z.-X.; Xiao, Q.; Ye, Q.-D.; Sun, T.-W.; Meng, F.-K.; Ren, W.-W.; You, L.; Xu, L.-M.; Wang, Y.-F.; Chen, J.-H.; Yang, Z. Diastereoselective total synthesis of WWWWW-schindilactone A, part 2: construction of the fully functionalized CDEFGH ring system. Chem. Asian J., 2012, 7, 2334-2340
151. Ren, W.-W.; Chen, Z.-X.; Xiao, Q.; Li, Y.; Sun, T.-W.; Zhang, Z.-Y.; Ye, Q.-D.; Meng, F.-K.; You, L.; Zhao, M.-Z.; Xu, L.-M.; Tang, Y.-F.; Chen, J.-H.; Yang, Z. Diastereoselective total synthesis of DDDDD-schindilactone A, part 3: the final phase and completion. Chem. Asian J., 2012, 7, 2341-2350
152. Tang, Y.; Zhang, Y.; Dai, M.; Luo, T.; Deng, L.; Chen, J.; Yang, Z. A highly efficient synthesis of the FGH ring of micrandilactone A. Application of thioureas as ligands in the Co-catalyzed Pauson-Khand reaction and Pd-catalyzed carbonylative annulation. Org. Lett., 2005, 7, 885-888.
153. 8-catalyzed Pauson-Khand reaction under balloon pressure of CO. Org. Lett., 2005, 7, 593-595
154. Tang, Y.; Deng, L.; Zhang, Y.; Dong, G.; Chen, J.; Yang, Z. Thioureas as ligands in the Pd-catalyzed intramolecular Pauson-Khand reaction. Org. Lett., 2005, 7, 1657-1659.
155. Li, Z.; Gao, Y.; Jiao, Z.; Wu, N.; Wang, D. Z.; Yang, Z. Diversity-oriented synthesis of fused pyran sslactones via an efficient Pd-thiourea-catalyzed alkoxycarbonylative annulation. Org. Lett., 2008, 10, 5163-5166.
156. Exon, C.; Magnus, P. Stereoselectivity of intramolecular dicobalt octacarbonyl alkene-alkyne cyclizations: short synthesis of dl-coriolin. J. Am. Chem. Soc., 1983, 105, 2477-2478.
157. Magnus, P.; Rivera, H.; Lynch, V. Concise formal total synthesis of platensimycin mediated by a stereoselective autooxidation and hydroxyl group directed conjugative reduction. Org. Lett., 2010, 12, 5677-5680.
158. Sandeep, T. C.; Yau, J. L. W.; MacLullich, A. M. J.; Noble, J.; Deary, I. J.; Walker, B. R.; Seckl, J. R. 11WWHydroxysteroid dehydrogenase inhibition improves cognitive function in healthy elderly men and type 2 diabetics. Proc. Natl. Acad. Sci., 2004, 101, 6734-6739.
159. Chrousos, G. P. Is 11hydroxysteroid dehydrogenase type I a good therapeutic target for blockade of glucocorticoid actions? Proc. Natl. Acad. Sci., 2004, 101, 6329-6330.
160. Sawada, T.; Nakada, M. Enantioselective total synthesis of (+)-colletoic acid via catalytic asymmetric intramolecular cyclopropanation of an nndiazodddketo diphenylphosphine oxide. Org. Lett., 2013, 15, 1004-1007
161. Ling, T.; Griffith, E.; Mitachi, K.; Rivas, F. Scalable and divergent total synthesis of sss-colletoic acid, a selective 11--hydroxysteroid dehydrogenase type 1 inhibitor. Org. Lett., 2013, In Press.
162. Honma, M.; Sawada, T.; Fujisawa, Y.; Utsugi, M.; Watanabe, H.; Umino, A.; Matsumura, T.; Hagihara, T.; Takano, M.; Nakada, M. Asymmetric catalysis on the intramolecular cyclopropanation of oodiazodddketo sulfones. J. Am. Chem. Soc., 2003, 125, 2860-2861.
163. Burch, P.; Binaghi, M.; Scherer, M.; Wentzel, C.; Bossert, D.; Eberhardt, L.; Neuburger, M.; Scheiffele, P.; Gademann, K. Total synthesis of gelsemiol. Chem. Eur. J., 2013, 19, 2589-2591.
164. Markó, I.; Warriner, S. L.; Augustyns, B. Radical-initiated, skeletal rearrangements of bicyclo[2.2.2]lactones. Org. Lett., 2000, 2, 3123-3125
165. Augustyns, B.; Maulide, N.; Markó, I. Skeletal rearrangements of bicyclo[2.2.2]lactones: a short and efficient route towards Corey's lactone. Tet. Lett., 2005, 46, 3895-3899
166. Liao, J.-H.; Maulide, N.; Augustyns, B.; Markó, I. Tandem radical rearrangements/Pd-catalysed translocation of bicyclo[2.2.2]lactones. An efficient access to the oxa-triquinane core structure. Org. Biomol. Chem., 2006, 4, 1464-1467.
167. He, W.; Huang, J.; Sun, X.; Frontier, A. J. Total synthesis of (+/-)-merrilactone A via catalytic Nazarov cyclization. J. Am. Chem. Soc., 2007, 129, 498-499
168. He, W.; Huang, J.; Sun, X.; Frontier, A. J. Total synthesis of ooooo-merrilactone A. J. Am. Chem. Soc., 2008, 130, 300-308.
169. The salen promoted enantioselective Nazarov cyclization of dienones was recently reported by Rawal's group: Hutson, G. E.; Türkmen, Y. E.; Rawal, V. H. Salen promoted enantioselective Nazarov cyclizations of activated and unactivated dienones. J. Am. Chem. Soc., 2013, 135, 4988-4991
170. For oxazolidinone-based stereocontrol over the torquoselectivity in an auxiliarydirected 444electrocyclic Nazarov ring closure, see: Flynn, B. L.; Manchala, N.; Krenske, E. H. Opposing auxiliary conformations produce the same torquoselectivity in an oxazolidinone-directed Nazarov cyclization. J. Am. Chem. Soc., 2013, 135, 9156-9163.
171. Leboeuf, D.; Wright, C. M.; Frontier, A. J. Reagent control of [1,2]-Wagner-Meerwein chemoselectivity following the Nazarov cyclization: application to the total synthesis of enokipodin B. Chem. Eur. J., 2013, 19, 4835-4841
172. Leboeuf, D.; Gandon, V.; Ciesielski, J.; Frontier, A. J. Experimental and theoretical studies on the Nazarov cyclization/Wagner-Meerwein rearrangement sequence. J. Am. Chem. Soc., 2012, 134, 6296-6308
173. Leboeuf, D.; Huang, J.; Gandon, V.; Frontier, A. J. Using Nazarov electrocyclization to stage chemoselective [1,2]-migrations: stereoselective synthesis of functionalized cyclopentenones. Angew. Chem. Int. Ed., 2011, 50, 10981-10985
174. Huang, J.; Leboeuf, D.; Frontier, A. J. Understanding the fate of the oxyallyl cation following Nazarov electrocyclization: sequential Wagner-Meerwein migrations and the synthesis of spirocyclic cyclopentenones. J. Am. Chem. Soc., 2011, 133, 6307-6317.
175. Kuwahara, S.; Saito, M. Enantioselective total synthesis of enokipodins A-D. Tet. Lett., 2004, 45, 5047-5049.
176. For a recent total synthesis of a related cyclopentanone natural product, cuparenone, see: Okamoto, R.; Tanaka, K. Rhodium-catalyzed olefin isomerization/allyl Claisen rearrangement/intramolecular hydroacylation cascade. Org. Lett., 2013, 15, 2112-2115.
177. Jansone-Popova, S.; May, J. A. Synthesis of bridged polycyclic ring systems via carbene cascades terminating in C-H bond insertion. J. Am. Chem. Soc., 2012, 134, 17877-17880.
178. Wang, H.; Kohler, P.; Overman, L. E.; Houk, K. N. Origins of stereoselectivities of dihydroxylations of cis-bicyclo[3.3.0]octenes. J. Am. Chem. Soc., 2012, 134, 16054-16058.
179. Gomez, C.; Gicquel, M.; Carry, J.-C.; Schio, L.; Retailleau, P.; Voituriez, A.; Marinetti, A. Phosphine-catalyzed synthesis of 3,3-spirocyclopenteneoxindoles from sssubstituted allenoates: systematic studies and targeted applications. J. Org. Chem., 2013, 78, 1488-1496
180. For the synthesis of neuritogenic pentalenones by [3+2] cycloaddition between allene-derived zwitterions and cyclopentenones, see: Dakas, P.-Y.; Parga, J. A.; Höing, S.; Schöler, H. R.; Sterneckert, J.; Kumar, K.; Waldmann, H. Discovery of neuritogenic compound classes inspired by natural products. Angew. Chem. Int. Ed., 2013, 52, 9576-9581.
181. Wang, H.; Houk, K. N. Torsional control of stereoselectivities in electrophilic additions and cycloadditions to alkenes. Chem. Sci. 2013, In Press
182. Cheong, P. H.-Y.; Yun, H.; Danishefsky, S. J.; Houk, K. N. Torsional steering controls the stereoselectivity of epoxidation in the guanacastepene A synthesis. Org. Lett., 2006, 8, 1513-1516.
183. Benowitz, A. B.; Fidanze, S.; Small, P. L. C.; Kishi, Y. Stereochemistry of the core structure of the mycolactones. J. Am. Chem. Soc., 2001, 123, 5128-5129
184. Fidanze, S.; Song, F.; Szlosek-Pinaud, M.; Small, P. L. C.; Kishi, Y. Complete structure of the mycolactones. J. Am. Chem. Soc., 2001, 123, 10117-10118.
185. Xing, Y.; Hande, S. M.; Kishi, Y. Photochemistry of mycolactone A/B, the causative toxin of Buruli ulcer. J. Am. Chem. Soc., 2012, 134, 19234-19239.
186. Ireland, C.; Scheuer, P. J. Photosynthetic marine mollusks: in vivo 14C incorporation into metabolites of the sacoglossan Placobranchus ocellatus. Science, 1979, 205, 922-923.
187. Miller, A. K.; Banghart, M. R.; Beaudry, C. M.; Suh, J. M.; Trauner, D. Development of novel Lewis acid catalyzed cycloisomerizations: synthesis of bicyclo[3.1.0]hexenes and cyclopentenones. Tetrahedron, 2003, 59, 8919-8930
188. Miller, A. K.; Byun, D. H.; Beaudry, C. M.; Trauner, D. The total synthesis of sss-crispatene. Proc. Natl. Acad. Sci., 2004, 101, 12019-12023.
189. Luzung, M. R.; Markham, J. P.; Toste, F. D. Catalytic isomerization of 1,5-enynes to bicyclo[3.1.0]hexenes. J. Am. Chem. Soc., 2004, 126, 10858-10859
190. Development of a substituted bicyclo[3.1.0]hexane dicarboxylate as a pharmacological tool compound to investigate metabotropic glutamate 2/3 receptor function: Monn, J. A.; Valli, M. J.; Massey, S. M.; Hao, J.; Reinhard, M. R.; Bures, M. G.; Heinz, B. A.; Wang, X.; Carter, J. H.; Getman, B. G.; Stephenson, G. A.; Herin, M.; Catlow, J. T.; Swanson, S.; Johnson, B. G.; McKinzie, D. L.; Henry, S. S. Synthesis and pharmacological characterization of 4-substituted-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylates: identification of new potent and selective metabotropic glutamate 2/3 receptor agonists. J. Med. Chem., 2013, 56, 4442-4455.
191. Miura, T.; Yadav, N. D.; Iwasaki, H.; Ozeki, M.; Kojima, N.; Yamashita, M. Novel skeleton transformation reaction of iipyrone derivatives to spirobicyclo[3.1.0]hexane derivatives using dimethylsulfoxonium methylide. Org. Lett., 2012, 14, 6048-6051.
192. Newhouse, T. R.; Kaib, P. S. J.; Gross, A. W.; Corey, E. J. Versatile approaches for the synthesis of fused-ring uulactones utilizing cyclopropane intermediates. Org. Lett., 2013, 15, 1591-1593.
193. Csatayová, K.; Davies, S. G.; Lee, J. A.; Ling, K. B.; Roberts, P. M.; Russell, A. J.; Thomson, J. E. Syntheses of trans-SCH-A and cis-SCH-A via a stereodivergent cyclopropanation protocol. Org. Lett., 2010, 12, 3152-3155
194. Hu, S.; Huang, Y.; Deshpande, M.; Luo, G.; Bruce, M. A.; Chen, L.; Mattson, G.; Iben, L. G.; Zhang, J.; Russell, J. W.; Clarke, W. J.; Hogan, J. B.; Ortiz, A.; Flint, O.; Henwood, A.; Gao, Q.; Antal-Zimanyi, I.; Poindexter, G. S. Discovery of a novel class of bicyclo[3.1.0]hexanylpiperazines as noncompetitive neuropeptide Y Y1 antagonists. ACS Med. Chem. Lett., 2012, 3, 222-226
195. Luo, G.; Chen, L.; Hu, S.; Huang, Y.; Mattson, G.; Iben, L. G.; Russell, J. W.; Clarke, W. J.; Hogan, J. B.; Antal-Zimanyi, I.; Poindexter, G. S. Heterocyclic modification of a novel bicyclo[3.1.0]hexane NPY1 receptor antagonist. Bioorg. Med. Chem. Lett., 2013, 23, 3814-3817
196. Miller, J. F.; Chong, P. Y.; Shotwell, J. B.; Catalano, J. G.; Tai, V. W.-F.; Fang, J.; Banka, A. L.; Roberts, C. D.; Youngman, M.; Zhang, H.; Xiong, Z.; Mathis, A.; Pouliot, J. J.; Hamatake, R. K.; Price, D. J.; Seal III, J. W.; Stroup, L. L.; Creech, K. L.; Carballo, L. H.; Todd, D.; Spaltenstein, A.; Furst, S.; Hong, Z.; Peat, A. J. Hepatitis C replication inhibitors that target the viral NS4B protein. J. Med. Chem., 2013, In Press.
197. Mohr, J. T.; Behenna, D. C.; Harned, A. M.; Stoltz, B. M. Angew. Chem. Int. Ed., 2000, 39, 3494-3497
198. Behenna, D. C.; Stoltz, B. M. The enantioselective Tsuji allylation. J. Am. Chem. Soc., 2004, 126, 15044-15045.
199. Seto, M.; Roizen, J. L.; Stoltz, B. M. Catalytic enantioselective alkylation of substituted dioxanone enol ethers: ready access to C(o)-tetrasubstituted hydroxyketones, acids, and esters. Angew. Chem. Int. Ed., 2008, 47, 6873-6876
200. Craig, R. A.; Roizen, J. L.; Smith, R. C.; Jones, A. C.; Stoltz, B. M. Enantioselective synthesis of a hydroxymethyl-cis-1,3-cyclopentenediol building block. Org. Lett., 2012, 14, 5716-5719.
201. Hong, A. Y.; Krout, M. R.; Jensen, T.; Bennett, N. B.; Harned, A. M.; Stoltz, B. M. Ring-contraction strategy for the practical, scalable, catalytic asymmetric synthesis of versatile aaquaternary acylcyclopentenes. Angew. Chem. Int. Ed., 2011, 50, 2756-2760
202. Hong, A. Y.; Bennett, N. B.; Krout, M. R.; Jensen, T.; Harned, A. M.; Stoltz, B. M. Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters. Tetrahedron, 2011, 67, 10234-10248.
203. Aikawa, K.; Okamoto, T.; Mikami, K. Copper(I)-catalyzed asymmetric desymmetrization: synthesis of five-membered-ring compounds containing all-carbon quaternary stereocenters. J. Am. Chem. Soc., 2012, 134, 10329-10332.
204. Touré, B. B.; Hall, D. G. Natural product synthesis using multicomponent reaction strategies. Chem. Rev., 2009, 109, 4439-4486
205. 3B-mediated radical-polar crossover reaction for single-step coupling of O, Te-acetal, aaaaunsaturated ketones, and aldehydes/ ketones. Org. Lett. 2013, 15, 5122-5125.
206. Saǧi{dotless}rli, A.; Dürüst, Y.; Kariuki, B.; Knight, D. W. A practical isocyanidebased multicomponent synthesis of polysubstituted cyclopentenes. Tetrahedron, 2013, 69, 69-72.
207. Williams, R. M.; Cao, J.; Tsujishima, H.; Cox, R. J. Asymmetric, stereocontrolled total synthesis of paraherquamide A. J. Am. Chem. Soc., 2003, 125, 12172-12178
208. Whyte, A. C.; Gloer, J. B.; Wicklow, D. T.; Dowd, P. F. Sclerotiamide: a new member of the paraherquamide class with potent antiinsectan activity from the sclerotia of Aspergillus sclerotiorum. J. Nat. Prod., 1996, 59, 1093-1095
209. Kong, K.; Enquist Jr., J. A.; McCallum, M. E.; Smith, G. M.; Matsumaru, T.; Menhaji-Klotz, E.; Wood, J. L. An enantioselective total synthesis and stereochemical revision of ttt-citrinadin B. J. Am. Chem. Soc., 2013, 135, 10890-10893
210. Li, X.; Li, Y.-M.; Peng, F.-Z.; Wu, S.-T.; Li, Z.-Q.; Sun, Z.-W.; Zhang, H.-B.; Shao, Z.-H. Highly enantioselective one-pot synthesis of spirocyclopentaneoxindoles containing the oxime group by organocatalyzed Michael addition/ISOC/fragmentation sequence. Org. Lett., 2011, 13, 6160-6163
211. Li, Y.-M.; Li, X.; Peng, F.-Z.; Li, Z.-Q.; Wu, S.-T.; Sun, Z.-W.; Zhang, H.-B.; Shao, Z.-H. Catalytic asymmetric construction of spirocyclopentaneoxindoles by a combined Ru-catalyzed cross-metathesis/double Michael addition sequence. Org. Lett., 2011, 13, 6200-6203.
212. Y. Zhao, L. Liu, W. Sun, J. Lu, D. McEachern, X. Li, S. Yu, D. Bernard, P. Ochsenbein, V. Ferey, J.-C. Carry, J. R. Deschamps, D. Sun, S. Wang, Diastereomeric spirooxindoles as highly potent and efficacious MDM2 inhibitors. J. Am. Chem. Soc. 2013, 135, 7223-7234
213. Zhao, Y.; Yu, S.; Sun, W.; Liu, L.; Lu, J.; McEachern, D.; Shargary, S.; Bernard, D.; Li, X.; Zhao, T.; Zou, P.; Sun, D.; Wang, S. A potent small-molecule inhibitor of the MDM2-p53 interaction (MI-888) achieved complete and durable tumor regression in mice. J. Med. Chem. 2013, 56, 5553-5561.
214. Albertshofer, K.; Anderson, K. E.; Barbas III, C. F. Assembly of spirooxindole derivatives via organocatalytic iminium-enamine cascade reactions. Org. Lett., 2012, 14, 5968-5971
215. For the asymmetric construction of structurally related spirocyclopentenebenzofuranones, see: Albertshofer, K.; Tan, B.; Barbas III, C. F. Asymmetric construction of spirocyclopentenebenzofuranone core structures via highly selective phosphine-catalyzed [3+2] cycloaddition reactions. Org. Lett., 2013, 15, 2958-2961.
216. Trost, B. M. [3+2] cycloaddition approaches to five-membered rings via trimethylenemethane and its equivalents. Angew. Chem. Int. Ed., 1986, 25, 1-20
217. Trost, B. M. Transition metal templates as guides for cycloadditions. Pure Appl. Chem., 1988, 60, 1615-1626.
218. Gordon, D. J.; Fenske, R. F.; Nanninga, T. N.; Trost, B. M. A molecular orbital study of substituted trimethylenemethane-bis(phosphine)palladium complexes. J. Am. Chem. Soc., 1981, 103, 5974-5976.
219. Trost, B. M.; Cramer, N.; Silverman, S. M. Enantioselective construction of spirocyclic oxindolic cyclopentanes by palladium-catalyzed trimethylenemethane-[3+2]-cycloaddition. J. Am. Chem. Soc., 2007, 129, 12396-12397
220. Trost, B. M.; Bringley, D. A.; Zhang, T.; Cramer, N. Rapid access to spirocyclic oxindole alkaloids: application of the asymmetric palladiumcatalyzed [3+2] trimethylenemethane cycloaddition. J. Am. Chem. Soc. 2013, In Press.
221. Peng, J.-B.; Qi, Y.; Ma, A.-J.; Tu, Y.-Q.; Zhang, F.-M.; Wang, S.-H.; Zhang, S.-Y. Cascade oxidative dearomatization/semipinacol rearrangement: an approach to 2-spirocyclo-3-oxindole derivatives. Chem. Asian J., 2013, 8, 883-887.
222. Crosby, J.; Stone, R.; Lienhard, G. E. Mechanisms of thiamine-catalyzed reactions. Decarboxylation of 2-(1-carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium chloride. J. Am. Chem. Soc. 1970, 92, 2891-2900
223. Crosby, J.; Lienhard, G. E. Mechanisms of thiamine-catalyzed reactions. Kinetic analysis of the decarboxylation of pyruvate by 3,4-dimethylthiazolium ion in water and ethanol. J. Am. Chem. Soc., 1970, 92, 5707-5716.
224. Ugai, T.; Tanaka, S.; Dokawa, S. A new catalyst for acyloin condensation. J. Pharm. Soc. Jpn., 1943, 63, 296-300.
225. Breslow, R. On the mechanism of thiamine action. IV. Evidence from studies on model systems. J. Am. Chem. Soc., 1958, 80, 3719-3726.
226. Grossmann, A.; Enders, D. N-heterocyclic carbene catalyzed domino reactions. Angew. Chem. Int. Ed., 2012, 51, 314-325
227. For a remarkable example of NHC-catalyzed generation of formal formaldehyde-derived acyl anions from biomass-derived carbohydrates, see: Zhang, J.; Xing, C.; Tiwari, B.; Chi, Y. R. Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones. J. Am. Chem. Soc., 2013, 135, 8113-8116.
228. Burstein, C.; Glorius, F. Organocatalyzed conjugate umpolung of unsaturated aldehydes for the synthesis of uubutyrolactones. Angew. Chem. Int. Ed., 2004, 43, 6205-6208.
229. He, M.; Bode, J. W. Catalytic synthesis of HHlactams via direct annulations of enals and N-sulfonylimines. Org. Lett., 2005, 7, 3131-3134.
230. Nair, V.; Menon, R. S.; Biju, A. T.; Sinu, C. R.; Paul, R. R.; Jose, A.; Sreekumar, V. Employing homoenolates generated by NHC catalysis in carbon-carbon bond-forming reactions: state of the art. Chem. Soc. Rev., 2011, 40, 5336-5346
231. For a recent report describing the asymmetric NHCcatalyzed addition of homoenolates to nitroalkenes, see: White, N. A.; Di-Rocco, D. A.; Rovis, T. Asymmetric N-heterocyclic carbene catalyzed addition of enals to nitroalkenes: controlling stereochemistry via the homoenolate reactivity pathway to access rrlactams. J. Am. Chem. Soc., 2013, 135, 8504-8507.
232. Nair, V.; Vellalath, S.; Poonoth, M.; Suresh, E. N-Heterocyclic carbenecatalyzed reaction of chalcones and enals via homoenolate: an efficient synthesis of 1,3,4-trisubstituted cyclopentenes. J. Am. Chem. Soc., 2006, 128, 8736-8737
233. Nair, V.; Babu, B. P.; Vellalath, S.; Varghese, V.; Raveendran, A. E.; Suresh, E. Nucleophilic heterocyclic carbene catalyzed annulation of enals to chalcones in methanol: a stereoselective synthesis of highly functionalized cyclopentanes. Org. Lett., 2009, 11, 2507-2510
234. Nair, V.; Babu, B. P.; Vellalath, S.; Suresh, E. Stereoselective synthesis of spirocyclopentanones via N-heterocyclic carbene-catalyzed reactions of enals and dienones. Chem. Commun., 2008, 747-749
235. Paul, R. R.; Lakshmi, K. C. S.; Suresh, E.; Nair, V. NHC-catalysed annulation of enals to ene-1,4-diones: stereoselective synthesis of 1,3-diaryl-4-acyl cyclopentenes. Tet. Lett., 2013, 54, 2046-2049
236. Jose, A.; Lakshmi, K. C. S.; Suresh, E.; Nair, V. Phosphine-mediated reaction of 3-alkyl allenoates and diaryl 1,2-diones: efficient diastereoselective synthesis of fully substituted cyclopentenones. Org. Lett., 2013, 15, 1858-1861.
237. Cardinal-David, B.; Raup, D. E. A.; Scheidt, K. A. Cooperative Nheterocyclic carbene/Lewis acid catalysis for highly stereoselective annulation reactions with homoenolates. J. Am. Chem. Soc., 2010, 132, 5345-5347
238. Cohen, D. T.; Cardinal-David, B.; Scheidt, K. A. Lewis acid activated synthesis of highly substituted cyclopentanes by the N-hetereocyclic carbene catalyzed addition of homoenolate equivalents to unsaturated ketoesters. Angew. Chem. Int. Ed., 2011, 50, 1678-1682
239. Wadamoto, M.; Phillips, E. M.; Reynolds, T. E.; Scheidt, K. A. Enantioselective synthesis of MMMMdisubstituted cyclopentenes by an N-hetereocyclic carbene-catalyzed desymmetrization of 1,3-diketones. J. Am. Chem. Soc., 2007, 129, 10098-10099.
240. Chiang, P.-C.; Kaeobamrung, J.; Bode, J. W. Enantioselective, cyclopenteneforming annulations via NHC-catalyzed benzoin-oxy-Cope reactions. J. Am. Chem. Soc., 2007, 129, 3520-3521.
241. He, M.; Bode, J. W. Enantioselective, NHC-catalyzed bicycle-iilactam formation via direct annulations of enals and unsaturated N-sulfonyl ketimines. J. Am. Chem. Soc., 2008, 130, 418-419
242. Chiang, P.-C.; Rommel, M.; Bode, J. W. α-Hydroxyenones as mechanistic probes and scope-expanding surrogates for aaaaunsaturated aldehydes in N-heterocyclic carbenecatalyzed reactions. J. Am. Chem. Soc., 2009, 131, 8714-8718.
243. Kaeobamrung, J.; Bode, J. W. Stereodivergency of triazolium and imidazolium-derived NHCs for catalytic, enantioselective cyclopentane synthesis. Org. Lett., 2009, 11, 677-680.
244. Candish, L.; Lupton, D. W. N-Heterocyclic carbene-catalyzed Ireland-Coates Claisen rearrangement: synthesis of functionalized CClactones. J. Am. Chem. Soc., 2013, 135, 58-61.
245. Lathrop, S. P.; Rovis, T. Asymmetric synthesis of functionalized cyclopentanones via a multicatalytic secondary amine/N-heterocyclic carbene catalyzed cascade sequence. J. Am. Chem. Soc., 2009, 131, 13628-13630.
246. Enders, D.; Grossmann, A.; Huang, H.; Raabe, G. Dual secondary amine/Nheterocyclic carbene catalysis in the asymmetric Michael/cross-benzoin cascade reaction of rroxo sulfones with enals. Eur. J. Org. Chem., 2011, 4298-4301.
247. Hong, B.-C.; Dange, N. S.; Hsu, C.-S.; Liao, J.-H. Sequential organocatalytic Stetter and Micheal-aldol condensation reaction: asymmetric synthesis of fully substituted cyclopentenes via a [1+2+2] annulation strategy. Org. Lett., 2010, 12, 4812-4815
248. For a related domino Michael-aldol condensation approach to fully substituted cyclopentanones, see: Lefranc, A.; Guénée, L.; Alexakis, A. Highly diastereo-and enantioselective organocatalytic domino Michael/aldol reaction of acyclic 3-halogeno-1,2-diones to MMMMunsaturated aldehydes. Org. Lett., 2013, 15, 2172-2175.
249. Pham, P. V.; Ashton, K.; MacMillan, D. W. C. The intramolecular asymmetric allylation of aldehydes via organo-SOMO catalysis: a novel approach to ring construction. Chem. Sci., 2011, 2, 1470-1473
250. Mondal, S.; Bertrand, M. P.; Nechab, M. Enantioselective synthesis of carbocycles and heterocycles by radical/polar and polar/radical cascades. Angew. Chem. Int. Ed., 2013, 52, 809-811
251. Comito, R. J.; Finelli, F. G.; MacMillan, D. W. C. Enantioselective intramolecular aldehyde EEalkylation with simple olefins: direct access to homo-ene products. J. Am. Chem. Soc., 2013, 135, 9358-9361.
252. Li, M.; Datta, S.; Barber, D. M.; Dixon, D. J. Dual amine and palladium catalysis in diastereo-and enantioselective allene carbocyclization reactions. Org. Lett., 2012, 14, 6350-6353
253. Yang, T.; Ferrali, A.; Campbell, L.; Dixon, D. J. Combination iminium, enamine and copper(I) cascade catalysis: a carboannulation for the synthesis of cyclopentenes. Chem. Commun., 2008, 2923-2925.
254. Ma, G.; Afewerki, S.; Deiana, L.; Palo-Nieto, C.; Liu, L.; Sun, J.; Ibrahem, I.; Córdova, A. A palladium/chiral amine co-catalyzed enantioselective dynamic cascade reaction: synthesis of polysubstituted carbocycles with a quaternary carbon stereocenter. Angew. Chem. Int. Ed., 2013, 52, 6050-6054.
255. Kuwajima, I.; Kato, M. Base-induced rearrangement of 1-trimethylsilylpropargyl alcohol. Generation of lithiated trimethylsiloxyallenes and their reactions. Tet. Lett., 1980, 21, 623-626
256. Reich, H. J.; Olson, R. E.; Clark, M. C. Silyl ketone chemistry. Preparation of siloxyallenyland allyllithium reagents. J. Am. Chem. Soc., 1980, 102, 1423-1424.
257. Boyce, G. R.; Liu, S.; Johnson, J. S. Construction of cyclopentanol derivatives via three-component coupling of silyl glyoxylates, acetylides, and nitroalkenes. Org. Lett., 2012, 14, 652-655.
258. Shimizu, I.; Ohashi, Y.; Tsuji, J. Palladium-catalyzed [3+2] cycloaddition reaction of vinylcyclopropanes with rrrrunsaturated esters or ketones. Tet. Lett., 1985, 26, 3825-3828
259. For a recent example of cyclopentannulation of indoles with donor-acceptor cyclopropanes, see: Xiong, H.; Xu, H.; Liao, S.; Xie, Z.; Tang, Y. Copper-catalyzed highly enantioselective cyclopentannulation of indoles with donor-acceptor cyclopropanes. J. Am. Chem. Soc., 2013, 135, 7851-7854.
260. Trost, B. M.; Morris, P. J. Palladium-catalyzed diastereo-and enantioselective synthesis of substituted cyclopentanes through a dynamic kinetic asymmetric formal [3+2]-cycloaddition of vinyl cyclopropanes and alkylidene azlactones. Angew. Chem. Int. Ed., 2011, 50, 6167-6170
261. Trost, B. M.; Morris, P. J.; Sprague, S. J. Palladium-catalyzed diastereo-and enantioselective formal [3+2]-cycloadditions of substituted vinylcyclopropanes. J. Am. Chem. Soc., 2012, 134, 17823-17831.
262. Goldberg, A. F. G.; Stoltz, B. M. A palladium-catalyzed vinylcyclopropane [3+2] cycloaddition approach to the Melodinus alkaloids. Org. Lett., 2011, 13, 4474-4476.
263. Xu, H.; Qu, J.-P.; Liao, S.; Xiong, H.; Tang, Y. Highly enantioselective [3+2] annulation of cyclic enol ethers with donor-acceptor cyclopropanes: accessing 3aahydroxy [n.3.0]carbobicycles. Angew. Chem. Int. Ed., 2013, 52, 4004-4007.
264. Trost, B. M.; Stambuli, J. P.; Silverman, M.; Schwörer, U. Palladiumcatalyzed asymmetric [3+2] trimethylenemethane cycloaddition reactions. J. Am. Chem. Soc., 2006, 128, 13328-13329
265. Trost, B. M.; Silverman, S. M.; Stambuli, J. P. Development of an asymmetric trimethylenemethane cycloaddition reaction: application in the enantioselective synthesis of highly substituted carbocycles. J. Am. Chem. Soc., 2011, 133, 19483-19497
266. Trost, B. M.; Lam, T. M. Development of diamidophosphite ligands and their application to the palladium-catalyzed vinyl-substituted trimethylenemethane asymmetric [3+2] cycloaddition. J. Am. Chem. Soc., 2012, 134, 11319-11321.
267. Trost, B. M.; Maruniak, A. Enantioselectie construction of highly substituted vinylidenecyclopentanes by palladium-catalyzed asymmetric [3+2] cycloaddition reaction. Angew. Chem. Int. Ed., 2013, 52, 6262-6264.
268. Testero, S. A.; Mangione, M. I.; Suárez, A. G.; Spanevello, R. A. End-groupdifferentiating ozonolysis of norbornene systems to afford highly substituted cyclopentane rings. Eur. J. Org. Chem., 2013, 24, 5236-5245.
269. Hartung, J.; Grubbs, R. H. Highly Z-selective and enantioselective ringopening/ cross-metathesis catalyzed by a resolved stereogenic-at-Ru complex. J. Am. Chem. Soc., 2013, 135, 10183-10185.
270. Khan, R. K. M.; Torker, S.; Hoveyda, A. H. Readily accessible and easily modifiable Ru-based catalysts for efficient and Z-selective ring-opening metathesis polymerization and ring-opening/cross-metathesis. J. Am. Chem. Soc., 2013, 135, 10258-10261.
271. Zhang, C.; Lu, X. Phosphine-catalyzed cycloaddition of 2,3-butynoates with electron-deficient olefins. A novel [3+2] annulation approach to cyclopentenes. J. Org. Chem., 1995, 60, 2906-2909.
272. Fujiwara, Y.; Fu, G. C. Application of a new chiral phosphepine to the catalytic asymmetric synthesis of highly functionalized cyclopentenes that bear an array of heteroatom-substituted quaternary stereocenters. J. Am. Chem. Soc., 2011, 133, 12293-12297
273. Wilson, J. E.; Fu, G. C. Synthesis of functionalized cyclopentenes through catalytic asymmetric [3+2] cycloadditions of allenes with enones. Angew. Chem. Int. Ed., 2006, 45, 1426-1429
274. Han, X.; Wang, Y.; Zhong, F.; Lu, Y. Enantioselective [3+2] cycloaddition of allenes to acrylates catalyzed by dipeptide-derived phosphines: facile creation of functionalized cyclopentenes containing quaternary stereogenic centers. J. Am. Chem. Soc., 2011, 133, 1726-1729
275. Zhu, G.; Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. Aymmetric [3+2] cycloaddition of 2,3-butadienoates with electron-deficient olefins catalyzed by novel chiral 2,5-dialkyl-7-phenyl-7-phosphabicyclo[2.2.1]heptanes. J. Am. Chem. Soc., 1997, 119, 3836-3837
276. Cowen, B. J.; Miller, S. J. Enantioselective [3+2]-cycloadditions catalyzed by a protected, multifunctional phosphinecontaining ccamino acid. J. Am. Chem. Soc., 2007, 129, 10988-10989.
277. Parr, B. T.; Li, Z.; Davies, H. M. L. Asymmetric synthesis of highly functionalized cyclopentanes by a rhodium-and scandium-catalyzed five-step domino sequence. Chem. Sci., 2011, 2, 2378-2382.
278. Shealy, Y. F.; Clayton, J. D. 9-[β-DL-2α,3α-dihydroxy-4β-(hydroxymethyl)-cyclopentyl]adenine, the carbocyclic analog of adenosine. J. Am. Chem. Soc., 1966, 88, 3885-3887
279. Shealy, Y. F.; Clayton, J. D. Synthesis of carbocyclic analogs of purine ribonucleotides. J. Am. Chem. Soc., 1969, 91, 3075-3083.
280. Peel, M. R.; Sternbach, D. D.; Johnson, M. R. A short, enantioselective synthesis of the carbocyclic nucleoside carbovir. J. Org. Chem., 1991, 56, 4990-4993.
281. Crimmins, M. T.; King, B. W. An efficient approach to carbocyclic nucleosides: asymmetric synthesis of 1592U89, a potent inhibitor of HIV reverse transcriptase. J. Org. Chem., 1996, 61, 4192-4193
282. Crimmins, M. T.; King, B. W.; Zuercher, W. J.; Choy, A. L. An efficient, general asymmetric synthesis of carbocyclic nucleosides: application of an asymmetric aldol/ ring-closing metathesis strategy. J. Org. Chem., 2000, 65, 8499-8509
283. Trost, B. M.; Osipov, M.; Kaib, P. S. J.; Sorum, M. T. Acetoxy Meldrum's acid: a versatile acyl anion equivalent in the Pd-catalyzed asymmetric allylic alkylation. Org. Lett., 2011, 13, 3222-3225.
284. Conlon, D. A.; Jensen, M. S.; Palucki M.; Yasuda, N.; Um, J. M.; Yang, C.; Hartner, F. W.; Tsay, F.-R.; Hsiao, Y.; Pye, P.; Rivera, N. R.; Hughes, D. L. Stereoselective synthesis of an anti-HIV drug candidate. Chirality, 2005, 17, S149-S158.
285. Arjona, O.; Gómez, A. M.; López, J. C.; Plumet, J. Synthesis and conformational and biological aspects of carbosugars. Chem. Rev., 2007, 107, 1919-2036.
286. Nicolaou, K. C.; Pfefferkorn, J. A.; Roecker, A. J.; Cao, G.-Q.; Barluenga, S.; Mitchell, H. J. Natural product-like combinatorial libraries based on priviledged structures. 1. General principles and solid-phase synthesis of benzopyrans. J. Am. Chem. Soc., 2000, 122, 9939-9953
287. Nicolaou, K. C.; Pfefferkorn, J. A.; Mitchell, H. J.; Roecker, A. J.; Barluenga, S.; Cao, G.-Q.; Affleck, R. L.; Lillig, J. E. Natural product-like combinatorial libraries based on priviledged structures. 2. Construction of a 10,000-membered benzopyran library by directed split-and-pool chemistry using NanoKans and optical encoding. J. Am. Chem. Soc., 2000, 122, 9954-9967.
288. Kuethe, J. T.; Marcoux, J.-F.; Wong, A.; Wu, J.; Hillier, M. C.; Dormer, P. G.; Davies, I. W.; Hughes, D. L. Stereoselective preparation of a cyclopentane-based NK1 receptor antagonist bearing an unsymmetrically substituted Sec-Sec ether. J. Org. Chem., 2006, 71, 7378-7390
289. Keuthe, J. T.; Wong, A.; Wu, J.; Davies, I. W.; Dormer, P. G.; Welsh, C. J.; Hillier, M. C.; Hughes, D. L.; Reider, P. J. Asymmetric synthesis of 1,2,3-trisubstituted cyclopentanes and cyclohexanes as key components of substance P antagonists. J. Org. Chem., 2002, 67, 5993-6000.