Enantioselective synthesis of natural epoxyquinoids

Current Organic Synthesis

Volumn 10, Issue 1, 2013, Pages 2-42

  Pandolfi, Enrique ^a   Schapiro, Valeria ^a   Heguaburu, Viviana ^a   Labora, Maitia ^a  

^a UNIVERSIDAD DE LA REPÚBLICA   (Uruguay)

Author keywords

Chemocatalyst; Enantioselective; Enzymatic methods; Epoxyquinoids; Scyphostatin; Synthesis

Indexed keywords

EID: 84873171483     PISSN: 15701794     EISSN: None     Source Type: Journal    
DOI: 10.2174/157017913804810951     Document Type: Review

References (173)

1. Thebtaranonth, C.; Thebtaranonth, Y. Naturally occurring cyclohexene oxides. Acc. Chem. Res., 1986, 19, 84-90.
2. Balci, M.; Sütbeyaz, Y.; Seçen, H. Conduritols and related compounds. Tetrahedron, 1990, 46, 3715-3742.
3. Marco-Contelles, J.; Molina, M.T.; Anjum, S. Naturally occurring cyclohexane epoxides: sources, biological activities and synthesis. Chem. Rev., 2004, 104, 2857-2900.
4. Krohn, K. Natural Products derived from naphtalenoid precursor by oxidative dimerization. In: Prog. Chem. Org. Nat. Prod., Herz, W.; Falk, H.; Kirby, G. W.; Moore, R. E.; Tamm, C., Eds.; Spriger: New York, 2003; Vol. 85, p 1.
5. Miyashita, K.; Imanishi, T. Syntheses of natural products having an epoxyquinone structure. Chem. Rev., 2005, 105, 4515-4536.
6. Cai, Y.S.; Guo, Y.W.; Krohn, K.; Bach, G. Structure, bioactivities, biosynthetic relationships and chemical synthesis of the spirodioxynaphthalenes. Nat. Prod. Rep., 2010, 27, 1840-1870.
7. Yamamoto, I.; Mizuta, E.; Henmi, T.; Yamano, T.; Yamatodani, S. Epoformin, a new antibiotic produced by Penicillium claviforme. J. Takeda Res. Lab., 1973, 32, 532-538.
8. Nagasawa, H.; Suzuki, A.; Tamura, S. Isolation and structure of (+)-desoxyepiepoxydon and (+)-epiepoxydon, phytotoxic fungal metabolites. Agr. Biol. Chem., 1978, 42, 1303-1304.
9. Sakamura, S.; Niki, H.; Obata, Y.; Sakai, R.; Matsumoto, T. Isolation and structure of phytotoxic compounds produced by Phyllosticta sp. Agr. Biol. Chem., 1969, 33, 698-703.
10. Closse, A.; Mauli, R.; Sigg, H.P. Die konstitution von epoxydon. Helv. Chim. Acta, 1966, 49, 204-213.
11. Mennucci, B.; Claps, M.; Evidente, A.; Rosini, C. Absolute configuration of natural cyclohexene oxides by time dependent density functional theory calculation of the optical rotation: the absolute configuration of (-)-sphaeropsidone and (-)-episphaeropsidone revised. J. Org. Chem., 2007, 72, 6680-6691.
12. Higa, T.; Okuda, R.K.; Severns, R.M.; Scheuer, P.J.; He, C.H.; Changfu, X.; Clardy, J. Unprecedented constituents of a new species acorn worm. Tetrahedron, 1987, 43, 1063-1070.
13. Gong, Y.N.; Wang, X.; Wang, J.; Yang, Z.; Li, S.; Yang, J.; Liu, L.; Lei, X.; Shao, F. Chemical probing reveals insights into the signaling mechanism of inflammasome activation. Cell Res., 2010, 20, 1289-1305.
14. Jarvis, B.B.; Yatawara, C.S. Roritoxins. New macrocyclic trichothecenes from Myrothecium roridum. J. Org. Chem., 1986, 51, 2906-2910.
15. Kakeya, H.; Onose, R.; Koshino, H.; Yoshida, A.; Kobayashi, K.; Kageyama, S.I.; Osada, H. Epoxyquinol A, a highly functionalized pentaketide dimer with antiangiogenic activity isolated from fungal metabolites. J. Am. Chem. Soc., 2002, 124, 3496-3497.
16. Miyake, Y.; Kakeya, H.; Kataoka, T.; Osada, T.H. Epoxycyclohexenone inhibits Fas-mediated apoptosis by blocking activation of pro-caspase-8 in the death-inducing signaling complex. J. Biol. Chem., 2003, 278, 11213-11220.
17. Kakeya, H.; Miyake, Y.; Shoji, M.; Kishida, S.; Hayashi, Y.; Kataoka, T.; Osada, H. Novel non-peptide inhibitors targeting death receptor-mediated apoptosis. Bioorg. Med. Chem. Lett., 2003, 13, 3743-3746.
18. Mitsui, T.; Miyake, Y.; Kakeya, H.; Osada, H.; Kataoka, T. ECH, an epoxycyclohexenone derivative that specifically inhibits Fas ligand-dependent apoptosis in CTL-mediated cytotoxicity. J. Immunol, 2004, 172, 3428-3436.
19. Mitsui, T.; Miyake, Y.; Kakeya, H.; Hayashi, Y.; Osada, H.; Kataoka, T. RKTS-33, an epoxyxyclohexenone derivative that specifically inhibits Fas ligand-dependent apoptosis in CTL-mediated cytotoxicity. Biosci. Biotechnol. Biochem., 2005, 69, 1923-1928.
20. Nagata, T.; Ando, Y.; Hirota, A. Phytotoxins from tea gray blight fungi, Pestalotiopsis longiseta and Pestalotiopsis theae. Biosci. Biotechnol. Biochem., 1992, 56, 810-811.
21. Garlaschelli, L.; Magistrali, E.; Vidari, G.; Zuffardi, O. Tricholomenyns A and B, novel antimitotic acetylenic cyclohexenone derivatives from the fruiting bodies of Tricholoma acerbum. Tetrahedron Lett., 1995, 36, 5633-5636.
22. Ma, X.; Jury, J.C.; Banwell, M.G. Synthesis and reactivity of a putative biogenetic precursor to tricholomenyns B, C, D and E. Tetrahedron Lett., 2011, 52, 2192-2194.
23. Pimentel, M.R.; Molina, G.; Dionisio, A.P.; Maróstica, M.R.J.; Pastore, G.M. The use of endophytes to obtain bioactive compounds and their application in biotransformation process. Biotech. Res. Int., 2011, 2011: 576286.
24. Guo, B.; Wang, X.; Sun, X.; Tang, K. Bioactive natural products from endophytes: A review. Appl. Biochem. Microb., 2008, 44, 136-142.
25. Li, J.Y.; Harper, J.K.; Grant, D.M.; Tombe, B.O.; Bashyal, B.; Hess, W.M.; Strobel, G.A. Ambuic acid, a highly functionalized cyclohexenone with antifungal activity from Pestalotiopsis spp. and Monochaetia sp. Phytochemistry, 2001, 56, 463-468.
26. Ding, G.; Li, Y.; Fu, S.; Liu, S.; Wei, J.; Che, Y. Ambuic acid and torreyanic acid derivatives from the endolichenic fungus Pestalotiopsis sp. J. Nat. Prod., 2009, 72, 182-186.
27. Nakayama, J.; Uemura, Y.; Nishiguchi, K.; Yoshimura, N.; Igarashi, Y.; Sonomoto, K. Ambuic acid inhibits the biosynthesis of cyclic peptide quormones in gram-positive bacteria. Antimicrob. Agents Chemother., 2009, 53, 580-586.
28. Labora, M.; Heguaburu, V.; Pandolfi, E.; Schapiro, V. Asymmetric synthesis of a model compound for the cyclohexenone core of ambuic acid. Tetrahedron: Asymmetry, 2008, 19, 893-895.
29. Gehrt, A.; Erkel, G.; Anke, H.; Anke, T.; Sterner, O. New hexaketide inhibitors of eukaryotic signal transduction. Nat. Prod. Lett., 1997, 9, 259-264.
30. Gehrt, A.; Erkel, G.; Anke, T.; Sterner, O. Cycloepoxydon, 1-hydroxy-2-hydroxymethyl-3-pent-1-enylbenzene and 1-hydroxy-2-hydroxymethyl-3-pent-1,3-dienylbenzene, new inhibitors of eukaryotic signal transduction. J. Antibiot., 1998, 51, 455-463.
31. Koizumi, F.; Matsuda, Y.; Nakanishi, S. EI-1941-1 and-2, novel interleukin-1 converting enzyme inhibitors produced by Farrowia sp. E-1941: I. Biochemical characterization of EI-1941-1 and-2. J. Antibiot., 2003, 56, 464-469.
32. Koizumi, F.; Takahashi, Y.; Ishiguro, H.; Tanaka, R.; Ohtaki, S.; Yoshida, M.; Nakanishi, S.; Ikeda, S. Structure elucidation of EI-1941-1 and-2, novel interleukin-1β converting enzyme inhibitors produced by Farrowia sp. E-1941. Tetrahedron Lett., 2004, 45, 7419-7422.
33. Dinarello, C.A.; Wolff, S.M. Mechanisms of disease: the role of Interleukin-1 in disease. N. Engl. J. Med., 1993, 328, 106-113.
34. Tanaka, M.; Nara, F.; Suzuki-Konagai, K.; Hosoya, T.; Ogita, T. Structural elucidation of scyphostatin, an inhibitor of membrane-bound neutral sphingomyelinase. J. Am. Chem. Soc., 1997, 119, 7871-7872.
35. Wascholowski, V.; Giannis, A.; Pitsinos, E.N. Influence of the scyphostatin side chain on the mode of inhibition of neutral sphingomyelinase. ChemMedChem, 2006, 1, 718-721.
36. Klein, B. Y.; Kerem, Z.; Rojansky, N. LDL induces Saos2 osteoblasts death via Akt pathways responsive to a neutral sphingomyelinase inhibitor. J. Cell. Biochem., 2006, 98, 661-671.
37. Nara, U.; Tanaka, M.; Hosoya, T.; Suzuki-Konagai, K.; Ogita, T. Scyphostatin, a neutral sphingomyelinase inhibitor from a discomycete, Trichopeziza mollissima: taxonomy of the producing organism, fermentation, isolation, and physico-chemical properties. J. Antibiot., 1999, 52, 525-530.
38. Nara, U.; Tanaka, M.; Hosoya, T.; Suzuki-Konagai, K.; Ogita, T. Biological activities of scyphostatin, a neutral sphingomyelinase inhibitor from a discomycete, Trichopeziza mollissima. J. Antibiot., 1999, 52, 531-535.
39. Matsumoto, N.; Ariga, A.; To-E, S.; Nakamura, H.; Naoki Agata, N.; Hirano, S.; Inoue, J.; Umezawa, K. Synthesis of NF-κB activation inhibitors derived from epoxyquinomicin C. Bioorg. Med. Chem. Lett., 2000, 10, 865-869.
40. Umezawa, K. Inhibition of tumor growth by NF-κB inhibitors. Cancer Sci., 2006, 97, 990-995.
41. Suzuki, E.; Yamashita, S.; Umezawa, K. Role of NF-κB in thyroid cancer. Thyroid Cancer, 2011, 319-327.
42. Umezawa, K. Possible role of peritoneal NF-κB in peripheral inflammation and cancer: Lessons from the inhibitor DHMEQ. Biomed. Pharmacother., 2011, 65, 252-259.
43. Kubota, M.; Shimmura, S.; Kubota, S.; Miyashita, H.; Kato, N.; Noda, K.; Ozawa, Y.; Usui, T.; Ishida, S.; Umezawa, K.; Kurihara, T.; Tsubota, K. Hydrogen and N-acetyl-L-cysteine rescue oxidative stress-induced angiogenesis in a mouse corneal alkali-burn mode. Invest. Ophth. Vis. Sci., 2011, 52, 427-433.
44. Yasuda, A.; Kondo, S.; Nagumo, T.; Tsukamoto, H.; Mukudai, Y.; Umezawa, K.; Shintani, S. Anti-tumor activity of dehydroxymethylepoxyquinomicin against human oral squamous cell carcinoma cell lines in vitro and in vivo. Oral Oncol., 2011, 47, 334-339.
45. Nakamori, K.; Matsuuta, H.; Yoshihara, T.; Ichihara, A.; Koda, Y. Potato micro-tuber inducing substances from Lasiodiplodia theobromae. Phytochemistry, 1994, 35, 835-839.
46. Kitaoka, N.; Nabeta, K.; Matsuura, H. Isolation and structural elucidation of a new cyclohexenone compound from Lasiodiplodia theobromae. Biosci. Biotechnol. Biochem., 2009, 73, 1890-1892.
47. Kong, F.-J.; Li, Y.; Abe, J.; Liu, B.; Schaller, F.; Piotrowski, M.; Otagaki, S.; Takahashi, K.; Matsuura, H.; Yoshihara, T.; Nabeta, K. Expresion of allene oxide cyclase from Pharbitis nil upon theobroxide treatment. Biosci. Biotechnol. Biochem., 2009, 73, 1007-1013.
48. Takei, R.; Takahashi, K.; Matsuura, H.; Nabeta, K. New potato micro-tuberinducing cyclohexene compound related to theobroxide from Lasiodiplodia theobromae. Biosci. Biotechnol. Biochem., 2008, 72, 2069-2073.
49. Li, P.; Takei, R.; Takahashi, K.; Nabeta, K. Biosynthesis of theobroxide and its related compounds, metabolites of Lasiodiplodia theobromae. Phytochemistry, 2007, 68, 819-823.
50. Gao, X.; Wang, F.; Yang, Q.; Matsuura, H.; Yoshihara, T. Theobroxide triggers jasmonic acid production to induce potato tuberization in vitro. Plant Growth Regul., 2005, 47, 39-45.
51. Kong, F.; Gao, X.; Nam, K.H.; Takahashi, K.; Matsuura, H.; Yoshihara, T. Inhibition of stem elongation in spinach by theobroxide. J.Plant Physiol., 2006, 163, 557-561.
52. Mühlenfeld, A.; Achenbach, H. Asperpentyn, a novel acetylenic cyclohexene epoxide from Aspergilus duricaulis. Phytochemistry, 1988, 27, 3853-3855.
53. Liu, Z.; Jensen, P. R.; Fenical, W. A cyclic carbonate and related polyketides from a marine-derived fungus of the genus Phoma. Phytochemistry, 2003, 64, 571-574.
54. Mehta, G.; Roy, S. Enantioselective total synthesis of eupenoxide and phomoxide. Org. Lett., 2004, 6, 2389-2392.
55. Mehta, G.; Roy, S.; Davis, R.A. On the stereostructures of (+)-eupenoxide and (-)-3,4-dihydrophomoxide: a caveat on the spectral comparisons of oxygenated cyclohexenoids. Tetrahedron Lett., 2008, 49, 5162-5164.
56. Davis, R.A.; Andjic, V.; Kotiw, M.; Shivas, R.G. Phomoxins B and C: Polyketides from an endophytic fungus of the genus Eupenicillium. Phytochemistry, 2005, 66, 2771-2775.
57. Daia, J.; Hussaina, H.; Drägerb, S.; Schulzb, B.; Kurtánc, T.; Pescitellid, G.; Flörkea, U.; Krohna, K. Metabolites from the fungus Phoma sp. 7210, associated with Aizoon canariense. Nat. Prod. Comm., 2010, 5, 1175-1180.
58. Sowemimo, A.A.; Edrada-Ebel, R.; Ebel, R.; Proksch, P.; Omobuwajo, O. R.; Adesanya, S.A. Major constituents of the predominant endophytic fungi from the Nigerian plants Bryophyllum pinnatum, Morinda lucida and Jathropha gossypiifolia. Nat. Prod. Comm., 2008, 3, 1217-1222.
59. Herath, K.B.; Jayasuriya, H.; Bills, G.F.; Polishook, J.D.; Dombrowski, A.W.; Guan, Z.; Felock, P.J.; Hazuda, D.J.; Singh, S.B. Isolation, structure, absolute stereochemistry, and HIV-1 integrase inhibitory activity of integrasone, a novel fungal polyketide. J. Nat. Prod., 2004, 67, 872-874.
60. Sekiguchi, J.; Gaucher, G. M. Identification of phyllostine as an intermediate of the patulin pathway in Penicillium urticae. Biochemistry, 1978, 17, 1785-1791.
61. Risau, W. Mechanism of angiogenesis. Nature, 1997, 386, 671-674.
62. Kakeya, H.; Onose, R.; Yoshida, A.; Koshino, H.; Osada, H. Epoxyquinol B, a fungal metabolite with a potent antiangiogenic activity. J. Antibiot., 2002, 55, 829-831.
63. Kamiyama, H.; Usui, T.; Sakurai, H.; Shoji, M.; Hayashi, Y.; Kakeya, H.; Osada, H. Epoxyquinol B, a naturally occurring pentaketide dimer, inhibits NF-κB signaling by crosslinking TAK1. Biosci. Biotechnol. Biochem., 2008, 72, 1894-1900.
64. Shoji, M.; Hayashi, Y. Chemistry of epoxyquinols A, B, and C and epoxytwinol A. Eur. J. Org. Chem., 2007, 3783-3800.
65. Kakeya, H.; Onose, R.; Koshino, H.; Osada, H. Epoxytwinol A, a novel unique angiogenesis inhibitor with C2 symmetry, produced by a fungus. Chem. Commun., 2005, 20, 2575-2577.
66. Schlegel, B.; Härtl, A.; Dahse, H. M.; Gollmick, F.A.; Gräfe, U.; Dörfelt, H.; Kappes, B. Hexacyclinol, a new antiproliferative metabolite of Panus rudis HKI 0254. J. Antibiot., 2002, 55, 814-817.
67. Rychnovsky, S.D. Predicting NMR spectra by computational methods: Structure revision of hexacyclinol. Org. Lett., 2006, 8, 2895-2898.
68. Porco Jr., J. A.; Su, S.; Lei, X.; Bardhan, S.; Rychnovsky, S. D. Total synthesis and structure assignment of (+)-hexacyclinol. Angew. Chem. Int. Ed., 2006, 45, 5790-5792.
69. Saielli, G.; Bagno, A. Can two molecules have the same NMR spectrum? Hexacyclinol revisited. Org. Lett., 2009, 11, 1409-1412.
70. Sekizawa, R.; Ikeno, S.; Nakamura, H.; Naganawa, H.; Matsui, S.; Iinuma, H.; Takeuchi, T. Panepophenanthrin, from a mushroom strain, a novel inhibitor of the ubiquitin-activating enzyme. J. Nat. Prod., 2002, 65, 1491-1493.
71. Swinney, D.C. Targeting protein ubiquitination for drug discovery. What is in the drug discovery toolbox? Drug Discov. Today, 2001, 6, 244-250.
72. Matsuzawa, M.; Kakeya, H.; Yamaguchi, J.; Shoji, M.; Onose, R.; Osada, H.; Hayashi, Y. Enantio-and diastereoselective total synthesis of (+)-panepophenanthrin, a ubiquitin-activating enzyme inhibitor, and biological properties of its new derivatives. Chem. Asian J., 2006, 1, 845-851.
73. Encarnación, R.D.; Sandoval, E.; Malmstrøm, J.; Christophersen, C. Calafianin, a bromotyrosine derivative from the marine sponge Aplysina gerardogreeni. J. Nat. Prod., 2000, 63, 874-875.
74. Ogamino, T.; Nishiyama, S. Synthesis and structural revision of calafianin, a member of the spiroisoxazole family isolated from the marine sponge, Aplysina gerardogreeni. Tetrahedron Lett., 2005, 46, 1083-1086.
75. Lee, J.C.; Strobel, G.A.; Lobkovsky, E.; Clardy, J. Torreyanic acid: a selectively cytotoxic quinone dimer from the endophytic fungus Pestalotiopsis microspora. J. Org. Chem., 1996, 61, 3232-3233.
76. Gibson, D.T.; Hensley, M.; Yoshiota, H.; Mabry, T. J. Formation of (+)-cis-2,3-dihydroxy-1-methylcyclohexa-4,6-diene from toluene by Pseudomonas putida. Biochemistry, 1970, 9, 1626-1630.
77. Gibson, D.T.; Koch, J.; Kallio, R. Oxidative degradation of aromatic hydrocarbons by microorganisms. I. Enzymatic formation of catechol from benzene. Biochemistry, 1968, 7, 2653-2662.
78. Hudlicky, T.; González, D.; Gibson, D.T. Enzymatic dihydroxylation of aromatics in enantioselective synthesis: expanding asymmetric methodology. Aldrichim. Acta, 1999, 32, 35-62.
79. Banwell, M.G.; Edwards, A.J.; Hartfoot, G.J.; Jollife, K.A.; McLeod, M.D.; McRae, K.J.; Stewart, S.G.; Vogtle, M. Chemoenzymatic methods for the enantioselective preparation of sesquiterpenoid natural products from aromatic precursors. Pure Appl. Chem., 2003, 75, 223-229.
80. Johnson, R.A. Microbial arene oxidations. Org. React., 2004, 63, 117-264.
81. Hudlicky, T.; Reed, J.W. Celebrating 20 years of Synlett-Special account on the merits of biocatalysis and the impact of arene cis-dihydrodiols on enantioselective synthesis. Synlett, 2009, 685-703.
82. Schapiro, V.; Cavalli, G.; Seoane, G.; Faccio, R.; Mombrú, A. Chemoenzymatic synthesis of chiral enones from aromatic compounds. Tetrahedron: Asymmetry, 2002, 13, 2453-2459.
83. Pinkerton, D.M.; Banwell, M.G.; Willis, A.C. Chemoenzymatic access to versatile epoxyquinol synthons. Org. Lett., 2009, 11, 4290-4293.
84. Pinkerton, D.; Banwell, M.C.; Willis, A.C. Rapid, chemoenzymatic synthesis of epoxyquinols. Aus. J. Chem., 2009, 62, 1639-1645.
85. Labora, M.; Pandolfi, E.; Schapiro, V. Efficient enantiodivergent total synthesis of (+) and (-)-bromoxone. Tetrahedron: Asymmetry, 2010, 21, 153-155.
86. White, L.V.; Dietinger, C.E.; Pinkerton, D.M.; Willis, A.C.; Banwell, M.G. An enantioselective synthesis of the epoxyquinol (+)-isoepiepoformin. Eur. J. Org. Chem., 2010, 4365-4367.
87. Ma, X.; Jury, J.C.; Banwell, M.G. Synthesis and reactivity of a putative biogenetic precursor to tricholomenyns B, C, D and E. Tetrahedron Lett., 2011, 52, 2192-2194.
88. Tachihara, T.; Kitahara, T. Total synthesis of (+)-epiepoformin, (+)-epiepoxydon and (+)-bromoxone employing a useful chiral building block, ethyl (1R,2S)-5,5-ethylenedioxy-2-hydroxycyclohexanecarboxylate. Tetrahedron, 2003, 59, 1773-1780.
89. Arimoto, H.; Shimano, T.; Uemura, D. Concise synthesis of the plant growth regulator theobroxide. J. Agric. Food Chem., 2005, 53, 3863-3866.
90. Toribio, G.; Marjanet, G.; Alibés, R.; de March, P.; Font, J.; Bayón, P.; Figueredo, M. Divergent approach to gabosines and anhydrogabosines: enantioselective syntheses of (+)-epiepoformin, (+)-epoformin, (+)-gabosine A, and gabosines B and F. Eur. J. Org Chem., 2011, 1534-1543.
91. Alibés, R.; Bayón, P.; de March, P.; Figueredo, M.; Font, J. Ç.; Marjanet, G. Enantioselective synthesis and absolute configuration assignment of gabosine O. Synthesis of (+)-and (-)-gabosine N and (+)-and (-)-epigabosines N and O. Org. Lett., 2006, 8, 1617-1620.
92. Hamada, M.; Niitsu, Y.; Hiraoka, C.; Kozawa, I.; Higashi, T.; Shoji, M. Chemoenzymatic synthesis of the physiologically active stereoisomer of DHMEQ. Tetrahedron, 2010, 66, 7083-7087.
93. Macdonald, G.; Alcaraz, L.; Lewis, N.J.; Taylor, R.J.K. Asymmetric synthesis of the mC7N core of the manumycin family: preparation of (+)-MT 35214 and a formal total synthesis of (-)-alisamycin. Tetrahedron Lett., 1998, 39, 5433-5436.
94. Niitsu, Y.; Hakamata, M.; Goto, Y.; Higashi, T.; Shoji, M.; Sugaia, T.; Umezawa, K. Chemoenzymatic synthesis of (2R,3R,4R)-dehydroxymethylepoxyquinomicin (DHMEQ), a new activator of antioxidant transcription factor Nrf2. Org. Biomol. Chem., 2011, 9, 4635-4641.
95. Comméiras, L.; Moses, J.E.; Adlington, R.M.; Baldwin, J.E.; Cowley, A.R.; Baker, C.M.; Albrecht, B.; Grant, G. H. Synthesis of the epoxyquinol dimerpanepophenanthrin. Tetrahedron, 2006, 62, 9892-9901.
96. Block, O.; Klein, G.; Altenbach, H.; Brauer, D. New stereoselective route to the epoxyquinone core of manumycin-type natural products. Synthesis of enantiopure (+)-bromoxone, (-)-LLC10037α and (+)kT8110. J. Org. Chem., 2000, 65, 716-721.
97. Mehta, G.; Srikrishna, A.; Reddy, A.V.; Nair, M.S. A novel, versatile synthetic approach to linearly fused tricyclopentanoids via-photo-thermal olefin metathesis. Tetrahedron, 1981, 37, 4543-4559.
98. Mehta, G.; Islam, K. Total synthesis of the novel NF-κB inhibitor (-)-cycloepoxydon. Org. Lett., 2004, 6, 807-810.
99. Mehta, G.; Islam, K. Total synthesis of the novel angiogenesis inhibitors epoxyquinols A and B. Tetrahedron Lett., 2003, 44, 3569-3572.
100. Mehta, G.; Islam, K. Enantioselective total synthesis of (-)-epoxyquinols A and B. Novel, convenient access to chiral epoxyquinone building blocks through enzymatic desymmetrization. Tetrahedron Lett., 2004, 45, 3611-3615.
101. Duke, R.K.; Rickards, R.W. Stereospecific total synthesis of the cyclohexene oxide antibiotic eupenoxide. J. Org. Chem., 1984, 49, 1898-1904.
102. Mehta, G.; Roy, S. Enantioselective total synthesis of a novel polyketide natural product (+)-integrasone, an HIV-1 integrase inhibitor. Chem. Commun., 2005, 3210-3212.
103. Mehta, G.; Roy, S. Enantioselective total synthesis of the polyketide natural product (-)-EI-1941-2: a novel interleukin-1β converting enzyme (ICE) inhibitor. Tetrahedron Lett., 2005, 46, 7927-7930.
104. Mehta, G.; Islam, K. Enantioselective total synthesis of epoxyquinone natural products (-)-phyllostine, (+)-epoxydon, (+)-epiepoxydon and (-)-panepophenanthrin: access to versatile chiral building blocks through enzymatic kinetic resolution. Tetrahedron Lett., 2004, 45, 7683-7687.
105. Mehta, G.; Pujar, S.R.; Ramesh, S.S.; Islam, K. Enantioselective total synthesis of polyoxygenated cyclohexanoids: (+)-streptol, ent-RKTS-33 and putative '(+)-parasitenone'. Identity of parasitenone with (+)-epoxydon. Tetrahedron Lett., 2005, 46, 3373-3376.
106. Son, B.W.; Choi, J.S.; Kim, J.C.; Nam, K.W.; Kim, D.S.; Chung, H.Y.; Kang, J.S.; Choi, H.D. Parasitenone, a new epoxycyclohexenone related to gabosine from the marine-derived fungus Aspergillus parasiticus. J. Nat. Prod., 2002, 65, 794-795.
107. Mehta, G.; Roy, S. Enantioselective total synthesis of the novel antiproliferative metabolite (+)-hexacyclinol. Tetrahedron Lett., 2008, 49, 1458-1460.
108. Takano, S.; Higashi, Y.; Kamikubo, T.; Moriya, M.; Ogasawara, K. Enantiodivergent preparation of chiral 2,5-cyclohexadienone synthons. Synthesis, 1993, 10, 948-950.
109. Mehta, G.; Ramesh, S.S. Enantioselective total synthesis of (+)-panepophenantrin, a novel inhibitor of the ubiquitin-activating enzyme. Tetrahedron Lett., 2004, 45, 1985-1988.
110. Barros, M.T.; Matias, P.M.; Maycock, C.D.; Ventura, M.R. Aziridines as a protecting and directing group. Stereoselective synthesis of (+)-bromoxone. Org. Lett., 2003, 5 4321-4323.
111. Barros, M.T.; Maycock, C.D.; Ventura, M.R. Enantioselective total synthesis of (+)-eutypoxide B. J. Org. Chem., 1997, 62, 3984-3988.
112. Carreño, M.C.; Merino, E.; Ribagoda, M.; Somoza, A.; Urbano, A. Enantioselective synthesis of natural polyoxygenated cyclohexanes and cyclohexenes from [(p-tolylsulfinyl)methyl]-p-quinols. Chem. Eur. J., 2007, 13, 1064-1077.
113. Carreño, M.C.; Merino, E.; Ribagorda, M.; Somoza, A.; Urbano, A. Enantioselective synthesis of (+)-and (-)-dihydroepiepoformin and (+)-epiepoformin. Org. Lett., 2005, 7, 1419-1422.
114. Carreño, M.C.; Pérez-González, M.; Ribagoda, M.; Somoza, A.; Urbano, A. β-Hydroxysulfoxides as chiral cyclic ketone equivalents: Enantioselective synthesis of polysubstituted cyclohexanones, cyclohexenones and cyclohexenediones Chem. Commun., 2002, 24, 3052-3053.
115. Hookins, D.R.; Taylor, R.J.K. A double oxidation procedure for the preparation of halogen-substituted p-benzoquinone monoketals: asymmetric synthesis of (-)-harveynone. Tetrahedron Lett., 2010, 51, 6619-6621.
116. Li, C.; Pace, E.A.; Liang, M.; Lobkovsky, E.; Gilmore, T.D.; Porco Jr., J.A. Total synthesis of the NF-κB inhibitor (-)-cycloepoxydon: Utilization of tartrate-mediated nucleophilic epoxidation. J. Am. Chem. Soc., 2001, 123, 11308-11309.
117. Kleinke, A.S.; Li, C.; Rabasso, N.; Porco Jr., J.A. Total synthesis of the interleukin-1β converting enzyme inhibitor EI-1941-2 using tandem oxaelectrocyclization/ oxidation. Org. Lett., 2006, 8, 2847-2850.
118. Hu, Y.; Li, C.; Kulkarni, B.A.; Strobel, G.; Lobkovsky, E.; Torczynski, R. M.; Porco Jr., J.A. Exploring chemical diversity of epoxyquinoid natural products: Synthesis and biological activity of (-)-jesterone and related molecules. Org. Lett., 2001, 3, 1649-1652.
119. Shoji, M.; Uno, T.; Kakeya, H.; Onose, R.; Shiina, I.; Osada, H.; Hayashi, Y. Enantio-and diastereoselective total synthesis of EI-1941-1,-2, and-3, inhibitors of interleukin-1β converting enzyme, and biological properties of their derivatives. J. Org. Chem., 2005, 70, 9905-9915.
120. Li, C.; Johnson, R.P.; Porco Jr., J.A. Total synthesis of the quinone epoxide dimer (+)-torreyanic acid: application of a biomimetic oxidation/ electrocyclization/ Diels-Alder dimerization cascade. J. Am. Chem. Soc., 2003, 125, 5095-5106.
121. Li, C.; Bardhan, S.; Pace, E.A.; Liang, M.; Gilmore, T.D.; Porco Jr., J.A. Angiogenesis inhibitor epoxyquinol A: Total synthesis and inhibition of transcription factor NF-κB. Org. Lett., 2002, 4, 3267-3270.
122. Li, C.; Porco Jr., J.A. Synthesis of epoxyquinol A and related molecules: Probing chemical reactivity of epoxyquinol dimers and 2H-pyran precursors. J. Org. Chem., 2005, 70, 6053-6065.
123. Li, C.; Porco Jr., J.A. Synthesis of the epoxyquinol dimer RKB-3564 D: Utilization of an alkoxysilanol to promote [4+4] dimerization. J. Am. Chem. Soc., 2004, 126, 1310-1311.
124. Porco Jr., J.A.; Su, S.; Lei, X.; Bardhan, S.; Rychnovsky, S. D. Total synthesis and structure assignment of (+)-hexacyclinol. Angew. Chem. Int. Ed., 2006, 45, 5790-5792.
125. La Clair, J.J. Total syntheses of hexacyclinol, 5-epi-hexacyclinol, and desoxohexacyclinol unveil an antimalarial prodrug motif. Angew. Chem. Int. Ed., 2006, 45, 2769-2773.
126. Lei, X.; Johnson, R.P.; Porco Jr., J.A. Total synthesis of the ubiquitinactivating enzyme inhibitor (+)-panepophenanthrin. Angew. Chem. Int. Ed., 2003, 42, 3913-3917.
127. Bardhan, S.; Schmitt, D.C.; Porco Jr., J.A. Total synthesis and stereochemical assignment of the spiroisoxazoline natural product (+)-calafianin. Org. Lett., 2006, 8, 927-930.
128. Shoji, M.; Yamaguchi, J.; Kakeya, H.; Osada, H.; Hayashi, Y. Total synthesis of (+)-epoxyquinols A and B. Angew. Chem. Int. Ed., 2002, 41, 3192-3194.
129. Shoji, M. Total Synthesis of epoxyquinoid natural products. Bull. Chem. Soc. Jpn., 2007, 80, 1672-1690.
130. Shoji, M.; Imai, H.; Shiina, I.; Kakeya, H.; Osada, H.; Hayashi, Y. Different reaction modes for the oxidative dimerization of epoxyquinols and epoxyquinones. Importance of intermolecular hydrogen-bonding. J. Org. Chem., 2004, 69, 1548-1556.
131. Shoji, M.; Imai, H.; Mukaida, M.; Sakai, K.; Kakeya, H.; Osada, H.; Hayashi, Y. Total synthesis of epoxyquinols A, B, and C and epoxytwinol A and the reactivity of a 2H-pyran derivative as the diene component in the Diels-Alder reaction. J. Org. Chem., 2005, 70, 79-91.
132. Shoji, M.; Kishida, S.; Takeda, M.; Kakeya, H.; Osada, H.; Hayashi, Y. A practical total synthesis of both enantiomers of epoxyquinols A and B. Tetrahedron Lett., 2002, 43, 9155-9158.
133. Shoji, M.; Uno, T.; Hayashi, Y. Stereoselective total synthesis of ent-EI-1941-2 and epi-ent-EI-1941-2. Org. Lett., 2004, 6, 4535-4538.
134. Kuwahara, S.; Imada, S. Enantioselective total synthesis of antiangiogenic pentaketide dimers, epoxyquinols A and B, through an asymmetric aldol approach to their common monomeric precursor. Tetrahedron Lett., 2005, 46, 547-549.
135. Li, J.; Park, S.; Miller, R.L.; Lee, D. Tandem enyne metathesis-metallotropic [1,3]-shift for a concise total syntheses of (+)-asperpentyn, (-)-harveynone and (-)-tricholomenyn A. Org. Lett., 2009, 11, 571-574.
136. Li, J.; Lee, D. Application of a tandem metathesis to the synthesis of (+)-panepophenanthrin. Chem. Asian J., 2010, 5, 1298-1302.
137. Jin, M.Y.; Hwang, G.; Chae, H.I.; Jung, S.H.; Ryu, D. H. Highly efficient synthesis of (+)-bromoxone, (+)-epiepoxydon and (+)-epiepoformin. Bull. Korean Chem. Soc., 2010, 31, 727-730.
138. Lee, M.Y.; Kim, K.H.; Jiang, S.; Jung, Y.H.; Sim, J.Y.; Hwang, G.S.; Ryu, D.H. Enantioselective formal synthesis of antitumor agent (+)-ottelione A. Tetrahedron Lett, 2008, 49, 1965-1967.
139. Kamikubo, T.; Hiroya, K.; Ogasawara, K. Stereo-and enantio-controlled synthesis of two naturally occurring polyoxygenated cyclohexenemethanols, (+)-epiepoxydon and (-)-phyllostine, via catalytic asymmetrization of a meso substrate. Tetrahedron Lett., 1996, 37, 499-502.
140. Kamikubo, T.; Ogasawara, K. The enantiodivergent total synthesis of natural and unnatural enantiomers of theobroxide. Tetrahedron Lett., 1995, 36, 1685-1688.
141. Chae, H.I.; Hwang, G.S.; Jin, M.Y.; Ryu, D. H. Efficient asymmetric synthesis of chiral monomer of epoxyquinols and (-)-phyllostine. Bull. Korean Chem. Soc., 2010, 31, 1047-1050.
142. Clay, D.R.; Rosenberg, A.G.; McIntosh, M.C. Efficient, scalable asymmetric synthesis of an epoxy quinol via Noyori desymmetrization of a meso diketone. Tetrahedron: Asymmetry, 2011, 22, 713-716.
143. Inoue, M.; Yokota, W.; Murugesh, M. G.; Katoh, T. Total synthesis of (+)-scyphostatin, a potent and specific inhibitor of neutral sphingomyelinase. Angew. Chem. Int. Ed., 2004, 43, 4207-4209.
144. Corey, E.J.; Fuchs, P.L. Synthetic method for conversion of formyl groups into ethynyl groups Tetrahedron Lett., 1972, 13, 3769-3772.
145. Inoue, M.; Yokota, W.; Katoh, T. Enantioselective total synthesis of (+)-scyphostatin, a potent and specific inhibitor of neutral sphingomyelinase. Synthesis, 2007, 622-637.
146. Wang, A.X.; Miller, S.M.; Anderson, O.P.; Shi, Y. A class of C2 and pseudo C2 symmetric ketone catalysts for asymmetric epoxidation. conformational effect on catalysis. J. Org. Chem., 1999, 64, 6443-6458.
147. Watanabe, K.; Oguchi, T.; Takizawa, T.; Furuuchi, M.; Abe, H.; Katoh, T. Synthesis of scyphostatin analogs possessing various saturated fatty acid side-chains. Heterocycles, 2007, 73, 263-268.
148. Suzuki, T.; Ghozati, K.; Katoh, T.; Sasai, H. Ir-catalyzed oxidative desymmetrization of meso-diols. Org. Lett., 2009, 11, 4286-4288.
149. Claus, R.A.; Wustholz, A.; Muller, S.; Bockmeyer, C.L.; Riedel, N.H.; Kinscherf, R.; Deigner, H.P. Synthesis and antiapoptotic activity of a novel analogue of the neutral sphingomyelinase inhibitor scyphostatin. Chem. Bio. Chem., 2005, 6, 726-737.
150. Takagi, R.; Miyanaga, W.; Tojo, K.; Tsuyumine, S.; Ohkata, K. Stereoselective total synthesis of (+)-scyphostatin via π-facially selective Diels-Alder reaction. J. Org. Chem., 2007, 72, 4117-4125.
151. Wipf, P.; Kim, Y. A short, stereospecific synthesis of dihydrooxazoles from serine and threonine derivatives. Tetrahedron Lett., 1992, 33, 4117-4125.
152. Takagi, R.; Tsuyumine, S.; Miyanaga, W.; Ohkata, K. Stereoselective synthesis of the hydrophobic side chain of scyphostatin. Aust. J. Chem, 2004, 57, 439-447.
153. Takagi, R.; Tojo, K.; Iwata, M.; Ohkata, K. Synthesis of a 4,5-epoxy-2-cyclohexen-1-one derivative via epoxide ring opening, 1,3-carbonyl transposition and epoxide ring regeneration: a synthetic study on a scyphostatin analogue. Org. Biomol. Chem., 2005, 3, 2031-2036.
154. Miyanaga, W.; Takagi, R.; Ohkata, K. Synthetic study of an analogue of the hydrophilic moiety of scyphostatin via II facial selective Diels-Alder reaction. Heterocycles, 2004, 64, 75-91.
155. Pitsinos, E.N.; Moutsos, V.I.; Vageli, O. Synthesis of enantiopure (S)-7-hydroxy-3-amino-3,4-dihydro-2H-1-benzopyran en route to (+)-scyphostatin. Tetrahedron Lett., 2007, 48, 1523-1526.
156. Pitsinos, E.N.; Cruz, A. Short and efficient route to the fully functionalized polar core of scyphostatin. Org. Lett., 2005, 7, 2245-2248.
157. Green, R.; Taylor, P.J.M.; Bull, S.D.; James, T.D.; Mahon, M.F.; Merrit, A.T. A practical synthesis of enantiopure (S)-4-(4-hydroxybenzyl)-oxazolidin-2-one. Tetrahedron: Asymmetry, 2003, 14, 2619-2623.
158. Pitsinos, E.N.; Athinaios, N.; Xu, Z.; Wang, G.; Negishi, E. Total synthesis of (+)-scyphostatin featuring an enantioselective and highly efficient route to the side-chain via Zr-catalized asymmetric carboalumination of alkenes (ZACA). Chem. Commun., 2010, 46, 2200-2202.
159. Tan, Z.; Negishi, E.I. An efficient and general method for the synthesis of α,ω-difunctional reduced polypropionates by Zr-catalyzed asymmetric carboalumination: synthesis of the scyphostatin side chain. Angew. Chem. Int. Ed., 2004, 43, 2911-2914.
160. Fujioka, H.; Sawama, Y.; Kotoku, N.; Ohnaka, T.; Okitsu, T.; Murata, N.; Kubo, O.; Li, R.; Kita, Y. Concise asymmetric total synthesis of scyphostatin, a potent inhibitor of neutral sphimgomyelinase. Chem. Eur. J., 2007, 13, 10225-10238.
161. Hoye, T.R.; Tennakoon, M.A. Synthesis (and alternative proof of configuration) of the scyphostatin C(1')-C(20') trienoyl fragment. Org. Lett., 2000, 2, 1481-1483.
162. Hoye, T.R.; Jeffrey, C.S.; Nelson, D.P. Dynamic kinetic resolution during a vinylogous Payne rearrengement: a concise synthesis of the polar pharmacophoric subunit of (+)-scyphostatin. Org. Lett., 2010, 12, 52-55.
163. Cha, J.Y.; Burnett IV, L.; Huang, Y.; Davidson, J.B.; Pettus, T.R.R. A strategy for the late-stage divergent synthesis of scyphostatin analogs. J. Org. Chem., 2011, 76, 1361-1371.
164. Bunyapaiboonsri, T.; Yoiprommarat, S.; Intereya, K.; Rachtawee, P.; Hywel-Jones, N.L.; Isaka, M. Isariotins E and F, spirocyclic and bicyclic hemiacetals from the entomopathogenic fungus Isaria tenuipes BCC 12625. J. Nat. Prod., 2009, 72, 756-759.
165. Cha, J.Y.; Huang, Y.; Pettus, T.R.R. Total Synthesis of TK-57-164A, isariotin F, and their putative progenitor isariotin E. Angew. Chem. Int. Ed., 2009, 48, 9519-9521.
166. Hookins, D.R.; Burns, A.R.; Taylor, R.J.K. The first total syntheses of (+/-)-SDEF 678 metabolite and (+/-)-speciosins A-C. Eur. J. Org. Chem., 2011, 451-454.
167. Jiang, M.; Zhang, L.; Liu, R.; Dong, Z.; Liu, J. Speciosins A-K, oxygenated cyclohexanoids from the basidiomycete Hexagonia speciosa. J. Nat. Prod., 2009, 72, 1405-1409.
168. Kim, H.J.; Vinale, F.; Ghisalberti, E.L.; Worth, C.M.; Sivasithamparam, K.; Skelton, B.W.; White, A.H. An antifungal and plant growth promoting metabolite from a sterile dark ectotrophic fungus. Phytochemistry, 2006, 67, 2277-2280.
169. Bugni, T.S.; Abbanat, D.; Bernan, V.S.; Maiese, W.M.; Greenstein, M.; Van Wagoner, R.M.; Ireland, C.M. Yanuthones: novel metabolites from a marine isolate of Aspergillus niger. J. Org. Chem., 2000, 65, 7195-7200.
170. Li, X.; Choi, H.D.; Kang, J.S.; Lee, C.; Son, B.W. New polyoxygenated farnesylcyclohexenones, deacetoxyyanuthone A and its hydro derivative from the marine-derived fungus Penicillium sp. J. Nat. Prod., 2003, 66, 1499-1500.
171. Anderson, M.G.; Jarman, T.B.; Rickards, R.W. Structures and absolute configurations of antibiotics of the oligosporon group from the nematodetrapping fungus Arthrobotrys oligospora. J. Antibiot., 1995, 48, 391-398.
172. Mehta, G.; Pan, S.A. First total synthesis of yanuthones: novel farnesylated epoxycyclohexenoid marine natural products. Tetrahedron Lett., 2005, 46, 5219-5223.
173. Ding, G.; Zhang, F.; Chen, H.; Guo, L.; Zou, Z.; Che, Y. Pestaloquinols A and B, isoprenylated epoxyquinols frh pom Pestalotiopsis sp. J. Nat. Prod., 2011, 74, 286-291.