Recent developments in oxidative processes in steroid chemistry

Current Organic Chemistry

Volumn 16, Issue 10, 2012, Pages 1243-1276

  Salvador, Jorge A R ^a,b   Silvestre, Samuel M ^c   Moreira, Vânia M ^b  

^a UNIVERSITY OF COIMBRA   (Portugal)

^b UNIVERSITY OF COIMBRA   (Portugal)

^c UNIVERSITY OF BEIRA INTERIOR   (Portugal)

Author keywords

Alcohol oxidation; Allylic oxidation; Catalysis; Epoxidation; Oxidative processes; Remote functionalization; Steroids; Syndihydroxylation

Indexed keywords

CATALYSIS; EPOXIDATION; LIPIDS; SYNTHESIS (CHEMICAL);

ALCOHOL OXIDATION; ALLYLIC OXIDATION; BIOACTIVE COMPOUNDS; BIOLOGICALLY ACTIVE PRODUCTS; FUNCTIONALIZATIONS; OXIDATIVE PROCESS; OXYGENATED STEROIDS; REMOTE FUNCTIONALIZATION; STEROID; SYNDIHYDROXYLATION;

OXIDATION;

EID: 84861178831     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527212800564204     Document Type: Review

References (190)

1. Bäckvall, J.-E. Modern Oxidation Methods. Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2004.
2. 5-sterols. Lipids 2004, 39, 801-804.
3. 5-Steroids: Key-Molecules Owning Particular Biological and Chemical Interest. Mini Rev. Med. Chem. 2003, 3, 557-567.
4. Bulman Page, P. C.; McCarthy, T. J. In Comprehensive Organic Synthesis, Trost, B. M.; Flemming, I., Eds. Pergamon Press: Oxford-New York-Seoul-Tokyo, 1991; Vol. 7, pp 83-117.
5. 5-bile acids occurring in Niemann-Pick disease. Steroids 2009, 74, 766-772.
6. Brunel, J. M.; Loncle, C.; Vidal, N.; Dherbomez, M.; Letourneux, Y. Synthesis and antifungal activity of oxygenated cholesterol derivatives. Steroids 2005, 70, 907-912.
7. Rivera, D. G.; Concepción, O.; Pérez-Labrada, K.; Coll, F. Synthesis of diamino-furostan sapogenins and their use as scaffolds for positioning peptides in a preorganized form. Tetrahedron 2008, 64, 5298-5305.
8. Ricco, C.; Revial, G.; Ferroud, C.; Hennebert, O.; Morfin, R. Synthesis of 7β-hydroxy-epiandrosterone. Steroids 2011, 76, 28-30.
9. Salvador, J. A. R.; Silvestre, S. M.; Moreira, V. M. Catalytic oxidative processes in steroid chemistry: Allylic oxidation, β-selective epoxidation, alcohol oxidation and remote functionalization reactions. Curr. Org. Chem. 2006, 10, 2227-2257 and references cited therein.
10. 3F] (PSFC) Monatsh. Chem. 2008, 139, 521-523.
11. 5-Sterols Synth. Commun. 2009, 39, 1076-1083.
12. Silvestre, S. M.; Salvador, J. A. R. Allylic and benzylic oxidation reactions with sodium chlorite. Tetrahedron 2007, 63, 2439-2445.
13. Ochiai, M.; Ito, T.; Takahashi, H.; Nakanishi, A.; Toyonari, M.; Sueda, T.; Goto, S.; Shiro, M. Hypervalent (tert-Butylperoxy)iodanes Generate Iodine-Centered Radicals at Room Temperature in Solution: Oxidation and Deprotection of Benzyl and Allyl Ethers, and Evidence for Generation of α-Oxy Carbon Radicals. J. Am. Chem. Soc. 1996, 118, 7716-7730.
14. Zhao, Y.; Yeung, Y.-Y. An Unprecedented Method for the Generation of tert-Butylperoxy Radical Using DIB/TBHP Protocol: Solvent Effect and Application on Allylic Oxidation. Org. Lett. 2010, 12, 2128-2131.
15. 5-steroids with t-butyl hydroperoxide. J. Mol. Catal. A Chem. 2006, 250, 70-74.
16. VI-Catalyzed Benzylic, Allylic and Propargylic Oxidations by tert-Butyl Hydroperoxide. Mini Rev. Org. Chem. 2009, 6, 9-20.
17. Stephan, E. Synthesis of modified steroids in the androstane and androstene series. Org. Prep. Proc. Int. 2006, 38, 217-305 and references cited therein.
18. Shing, T. K. M.; Yeung, Y. Y.; Su, P. L. Mild manganese(III) acetate catalyzed allylic oxidation: Application to simple and complex alkenes. Org. Lett. 2006, 8, 3149-3151.
19. 5-steroids catalyzed by dirhodium caprolactamate. Org. Lett. 2007, 9, 5349-5352.
20. Yao, Z.; Hu, X.; Mao, J.; Li, H. An environmentally benign catalytic oxidation of cholesteryl acetate with molecular oxygen by using Nhydroxyphthalimide. Green Chem. 2009, 11, 2013-2017.
21. 5-Steroids Using tert-Butyl Hydroperoxide. J. Org. Chem. 2010, 75, 1807-1810.
22. Sugamoto, K.; Matsushita, Y.-i.; Yamamoto, T.; Matsui, T. Regioselective Hydroperoxygenation of Aralkanes and α,β-Unsaturated Carbonyl Compounds Catalyzed by N-Hydroxyphthalimide and 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile). Synth. Commun. 2005, 35, 1865-1874.
23. McLaughlin, E. C.; Choi, H.; Wang, K.; Chiou, G.; Doyle, M. P. Allylic Oxidations Catalyzed by Dirhodium Caprolactamate via Aqueous tert-Butyl Hydroperoxide: The Role of the tert-Butylperoxy Radical. J. Org. Chem. 2009, 74, 730-738.
24. Jiang, B.; Shi, H.-p.; Tian, W.-s.; Zhou, W.-s. The convergent synthesis of novel cytotoxic certonardosterol D2 from diosgenin. Tetrahedron 2008, 64, 469-476.
25. Jiang, B.; Shi, H. P.; Xu, M.; Wang, W. J.; Zhou, W. S. Stereoselective synthesis of certonardolsterol D-3. Tetrahedron 2008, 64, 9738-9744.
26. Williams, J. R.; Gong, H.; Hoff, N.; Olubodun, O. I. Synthesis of the Shark Repellent Pavoninin-4. J. Org. Chem. 2005, 70, 10732-10736.
27. Williams, J. R.; Gong, H. Biological activities and syntheses of steroidal saponins: the shark-repelling pavoninins. Lipids 2007, 42, 77-86.
28. Ogawa, S.; Wakatsuki, Y.; Makino, M.; Fujimoto, Y.; Yasukawa, K.; Kikuchi, T.; Ukiya, M.; Akihisa, T.; Iida, T. Oxyfunctionalization of unactivated C-H bonds in triterpenoids with tert-butylhydroperoxide catalyzed by meso-5,10,15,20-tetramesitylporphyrinate osmium(II) carbonyl complex. Chem. Phys. Lipids 2010, 163, 165-171.
29. Sello, G.; Fumagalli, T.; Orsini, F. Recent Developments in Epoxide Preparation. Curr. Org. Synth. 2006, 3, 379-402.
30. Kadis, B. Steroid epoxides in biologic systems: A review. J. Steroid Biochem. 1978, 9, 75-81.
31. Guardiola, F.; Dutta, P. C.; Codony, R.; Savage, G. P. Cholesterol and phytosterol oxidation products: analysis, occurrence, and biological effects. AOCS Press: Champaign, 2002.
32. Djurendic, E.; Daljev, J.; Sakac, M.; Canadi, J.; Santa, S. J.; Andric, S.; Klisuric, O.; Kojic, V.; Bogdanovic, G.; Djurendic-Brenesel, M.; Novakovic, S.; Gasi, K. P. Synthesis of some epoxy and/or N-oxy 17-picolyl and 17-picolinylidene-androst-5-ene derivatives and evaluation of their biological activity. Steroids 2008, 73, 129-138.
33. Bratoeff, E.; Segura, T.; Recillas, S.; Carrizales, E.; Palacios, A.; Heuze, I.; Cabeza, M. Aromatic esters of progesterone as 5α-reductase and prostate growth inhibitors. J. Enz. Inhib. Med. Chem. 2009, 24, 655-662.
34. Machin, R.; Veleiro, A. S.; Nicotra, V. E.; Oberti, J. C.; M. Padro, J. Antiproliferative Activity of Withanolides against Human Breast Cancer Cell Lines. J. Nat. Prod. 2010, 73, 966-968.
35. Duh, C.-Y.; Lo, I. W.; Wang, S.-K.; Dai, C.-F. New cytotoxic steroids from the soft coral Clavularia viridis. Steroids 2007, 72, 573-579.
36. Carvalho, J. F. S.; Silva, M. M. C.; Moreira, J. N.; Simoes, S.; Melo, M. Sterols as Anticancer Agents: Synthesis of Ring-B Oxygenated Steroids, Cytotoxic Profile, and Comprehensive SAR Analysis. J. Med. Chem. 2010, 53, 7632-7638.
37. Fried, J.; Edwards, J. A. Organic Reactions in Steroid Chemistry. Van Nostrand Reinold Company: New York, 1972.
38. Salvador, J. A. R.; Silvestre, S. M.; Moreira, V. M. Catalytic epoxidation and syn-dihydroxylation reactions in steroid chemistry. Curr. Org. Chem. 2008, 12, 492-522 and references cited therein.
39. Carvalho, J. F. S.; Silva, M. M. C.; Melo, M. Highly efficient epoxidation of unsaturated steroids using magnesium bis(monoperoxyphthalate) hexahydrate. Tetrahedron 2009, 65, 2773-2781.
40. Carvalho, J. F. S.; Silva, M. M. C.; Moreira, J. N.; Simoes, S.; Melo, M. Efficient Chemoenzymatic Synthesis, Cytotoxic Evaluation, and SAR of Epoxysterols. J. Med. Chem. 2009, 52, 4007-4019.
41. Ma, E.; Kim, H.; Kim, E. Epoxidation and reduction of cholesterol, 1,4,6-cholestatrien-3-one and 4,6-cholestadien-3β-ol. Steroids 2005, 70, 245-250.
42. Liu, P.; Wong, E. L.-M.; Yuen, A. W.-H.; Che, C.-M. Highly Efficient Alkene Epoxidation and Aziridination Catalyzed by Iron(II) Salt + 4,4′,4″-Trichloro-2,2′:6′,2″-terpyridine/4,4″-Dichloro-4′-O-PEG-OCH3-2,2′:6′,2″-terpyridine. Org. Lett. 2008, 10, 3275-3278.
43. 4-unsaturated steroids catalyzed by the silicasupported polyhalogenated ruthenium porphyrin. Appl. Catal. A: General 2006, 301, 176-181.
44. Krishna, V.; Chang, C. I.; Chou, C. H. Two isomeric epoxysitosterols from Rhododendron formosanum: H-1 and C-13 NMR chemical shift assignments. Magn. Res. Chem. 2006, 44, 817-819.
45. Luo, X.; Li, F.; Shinde, P. B.; Hong, J.; Lee, C.-O.; Im, K. S.; Jung, J. H. 26,27-Cyclosterols and other polyoxygenated sterols from a marine sponge Topsentia sp. J. Nat. Prod. 2006, 69, 1760-1768.
46. Mansoor, T. A.; Lee, Y. M.; Hong, J.; Lee, C.-O.; Im, K. S.; Jung, J. H. 5,6: 8,9-Diepoxy and other cytotoxic sterols from the marine sponge Homaxinella sp. J. Nat. Prod. 2006, 69, 131-134.
47. Ahmed, A. F.; Hsieh, Y.-T.; Wen, Z.-H.; Wu, Y.-C.; Sheu, J.-H. Polyoxygenated sterols from the formosan soft coral Sinularia gibberosa. J. Nat. Prod. 2006, 69, 1275-1279.
48. Su, J.-H.; Tseng, Y.-J.; Huang, H.-H.; Ahmed, A. F.; Lu, C.-K.; Wu, Y.-C.; Sheu, J.-H. 9,11-Secosterols from the Soft Corals Sinularia lochmodes and Sinularia leptoclados. J. Nat. Prod. 2006, 69, 850-852.
49. Ahmed, A. F.; Tai, S.-H.; Wu, Y.-C.; Sheu, J.-H. Sinugrandisterols A-D, trihydroxysteroids from the soft coral Sinularia grandilobata. Steroids 2007, 72, 368-374.
50. Drozdov, F. V.; Mekhtiev, A. P.; Morozevich, G. E.; Timofeev, V. P.; Misharina, A. Y. Cytotoxic Derivatives of (22R,23R)-Dihydroxystigmastane Russ. J. Bioorg. Chem. 2007, 33, 326.
51. Hong, B.-C.; Kim, S.; Kim, T.-S.; Corey, E. J. Synthesis and properties of several isomers of the cardioactive steroid ouabain. Tetrahedron Lett. 2006, 47, 2711-2715.
52. Hua, Z.; Carcache, D. A.; Tian, Y.; Li, Y.-M.; Danishefsky, S. J. The Synthesis and Preliminary Biological Evaluation of a Novel Steroid with Neurotrophic Activity: NGA0187. J. Org. Chem. 2005, 70, 9849-9856.
53. Li, M.; Yu, B. Facile Conversion of Spirostan Saponin into Furostan Saponin: Synthesis of Methyl Protodioscin and Its 26-Thio-analogue. Org. Lett. 2006, 8, 2679-2682.
54. Wang, H.; Su, F.; Zhou, L.; Chen, X.; Lei, P. Synthesis and cytotoxicities of icogenin analogues with disaccharide residues. Bioorg. Med. Chem. Lett. 2009, 19, 2796-2800.
55. Zheng, D.; Zhou, L.; Guan, Y.; Chen, X.; Zhou, W.; Chen, X.; Lei, P. Synthesis of cholestane glycosides bearing OSW-1 disaccharide or its 1-->4-linked analogue and their antitumor activities. Bioorg. Med. Chem. Lett. 2010, 20, 5439-5442.
56. Kocovsky, P. Stereochemistry of Epoxidation of Allylic and Homoallylic Cyclohexene Alcohols. J. Chem. Soc. Perkin Trans 1 1994, 1759-1763.
57. Glotter, E.; Mendelovici, M. Epoxidation Versus Oxidation of Steroidal Gamma-Hydroxy-Gamma-Beta-Unsaturated Ketones in Vanadium-Catalyzed Reactions. J. Chem. Res. (S) 1991, 214-215.
58. Foley, D. A.; O'Callaghan, Y.; O'Brien, N. M.; McCarthy, F. O.; Maguire, A. R. Synthesis and Characterization of Stigmasterol Oxidation Products. J. Agr. Food Chem. 2010, 58, 1165-1173.
59. Hang, J.; Dussault, P. A concise synthesis of β-sitosterol and other phytosterols. Steroids 2010, 75, 879-883.
60. Moghaddam, F. M.; Saeidian, H.; Mirjafary, Z.; Javan, M. J.; Farimani, M. M.; Seirafi, M. Convenient synthesis of chlorohydrins from epoxides using zinc oxide: Application to 5,6-epoxysitosterol. Heteroatom Chem. 2009, 20, 157-163.
61. Rosado-Abon, A.; Romero-Avila, M.; Iglesias-Arteaga, M. A. An unexpected and useful E-ring oxidative cleavage in furostanes. ARKIVOC 2008, xiv, 274-281.
62. Rosado-Abon, A.; Romero-Avila, M.; Iglesias-Arteaga, M. A. A rapid and simple one-pot procedure for the synthesis of 3β-acetoxy-5α-hydroxy-6-oxo steroids. ARKIVOC 2010, x, 110-115.
63. Baqi, Y.; Giroux, S.; Corey, E. J. A Study of the Epoxidation of Cycloolefins by the t-BuOH Copper-Permanganate System. Org. Lett. 2009, 11, 959-961.
64. Alam, M.; Mushfiq, M.; Naqvi, M. Transition Metal Salts Assisted Epoxidation of Cholestene Steroids. Oxidation Commun. 2009, 32, 321-329.
65. Zhang, J. L.; Huang, J. S.; Che, C. M. Oxidation chemistry of poly(ethylene glycol)-supported carbonylruthenium(II) and dioxoruthenium(VI) mesotetrakis(pentafluorophenyl)porphyrin. Chem. Eur. J. 2006, 12, 3020-3031.
66. 2-Supported Ru Monomer Complex Catalyst. J. Am. Chem. Soc. 2010, 132, 713-724.
67. A receptor activity of Ahomo analogues of neuroactive steroids. Eur. J. Med. Chem. 2010, 45, 3063-3069.
68. Kang, F.-A.; Allan, G.; Guan, J.; Jain, N.; Linton, O.; Tannenbaum, P.; Xu, J.; Zhu, P.; Gunnet, J.; Chen, X.; Demarest, K.; Lundeen, S.; Sui, Z. Synthesis and identification of novel oxa-steroids as progesterone receptor antagonists Bioorg. Med. Chem. Lett. 2007, 17, 907-910.
69. Jin, C.; Burgess, J. P.; Kepler, J. A.; Cook, C. E. Copper-Catalyzed Cyclization of Steroidal Acylaminoacetylenes: Syntheses of Novel 11β-Aryl-17,17-spiro[(4'H,5'-methylene)oxazol]-Substituted Steroids. Org. Lett. 2007, 9, 1887-1890.
70. 5(10),9(11)-diene Using Chiral Ammonium Salts Derived from Cinchona Alkaloids. Lett. Org. Chem. 2010, 7, 163-167.
71. Li, M.; Zhou, P. J.; Wu, A. M. Synthesis of Gymnasterone B, an antitumor steroid from Gymnascella dankaliensis. Tetrahedron Lett. 2006, 47, 3409-3412.
72. He, X.; Tang, J.; Qiao, A.; Wang, G.; Jiang, M.; Liu, R. H.; Yao, X. Cytotoxic biotransformed products from cinobufagin by Mucor spinosus and Aspergillus Niger. Steroids 2006, 71, 392-402.
73. Mitsui, K.; Saito, H.; Yamamura, R.; Fukaya, H.; Hitotsuyanagi, Y.; Takeya, K. Hydroxylated Gedunin Derivatives from Cedrela sinensis. J. Nat. Prod. 2006, 69, 1310-1314.
74. Jung, M. E.; Johnson, T. W. First total synthesis of xestobergsterol A and active structural analogues of the xestobergsterols. Tetrahedron 2001, 57, 1449-1481.
75. Calogeropoulou, T.; Avlonitis, N.; Minas, V.; Alexi, X.; Pantzou, A.; Charalampopoulos, I.; Zervou, M.; Vergou, V.; Katsanou, E. S.; Lazaridis, I.; Alexis, M. N.; Gravanis, A. Novel Dehydroepiandrosterone Derivatives with Antiapoptotic, Neuroprotective Activity. J. Med. Chem. 2009, 52, 6569-6587.
76. Lednicer, D.; Mitscher, L. A. In The Organic Chemistry of Drug Synthesis, Lednicer, D.; Mitscher, L. A., Eds. John Wiley & Sons, Inc.: New York-London-Sydney-Toronto, 1977; Vol. 1, pp 155-211.
77. Lednicer, D.; Mitscher, L. A. In The Organic Chemistry of Drug Synthesis, Lednicer, D.; Mitscher, L. A., Eds. John Wiley & Sons, Inc.: New York-Chichester-Brisbane-Toronto, 1980; Vol. 2, pp 135-206.
78. Lednicer, D.; Mitscher, L. A. In The Organic Chemistry of Drug Synthesis, Lednicer, D.; Mitscher, L. A., Eds. John Wiley & Sons, Inc.: New York-Chichester-Brisbane-Toronto-Singapore, 1984; Vol. 3, pp 81-108.
79. Lednicer, D.; Mitscher, L. A.; Georg, I. G. In The Organic Chemistry of Drug Synthesis, Lednicer, D.; Mitscher, L. A.; Georg, I. G., Eds. John Wiley & Sons, Inc.: New York-Chichester-Brisbane-Toronto-Singapore, 1990; Vol. 4, pp 65-77.
80. Lednicer, D. In The Organic Chemistry of Drug Synthesis, Lednicer, D., Ed. John Wiley & Sons, Inc.: New York-Chichester-Brisbane-Toronto-Singapore, 1995; Vol. 5, pp 48-63.
81. Lednicer, D. In Strategies for Organic Drug Synthesis and Design, Lednicer, D., Ed. John Wiley & Sons, Inc.: New York-Chichester-Weinheim-Brisbane-Singapore-Toronto, 1998; pp 84-145.
82. Fortner, K. C.; Kato, D.; Tanaka, Y.; Shair, M. D. Enantioselective Synthesis of (+)-Cephalostatin 1. J. Am. Chem. Soc. 2010, 132, 275-280.
83. Di Filippo, M.; Fezza, F.; Izzo, I.; De Riccardis, F.; Sodano, G. Novel Syntheses of (E)-and (Z)-Volkendousin, Cytotoxic Steroids from the Plant Melia volkensii. Eur. J. Org. Chem. 2000, 3247-3252.
84. Tang, P.; Yu, B. Total Synthesis of Candicanoside A, a Potent Antitumor Saponin with a Rearranged Steroid Side Chain. Angew. Chem. Int. Ed. 2007, 46, 2527-2530.
85. Tang, P.; Yu, B. Total Synthesis of Candicanoside A, a Rearranged Cholestane Disaccharide, and Its 4″-O-(p-Methoxybenzoate) Congener. Eur. J. Org. Chem. 2009, 259-269.
86. Eignerova, B.; Slavikova, B.; Budesinsky, M.; Dracinsky, M.; Klepetarova, B.; St'astna, E.; Kotora, M. Synthesis of Fluorinated Brassinosteroids Based on Alkene Cross-Metathesis and Preliminary Biological Assessment. J. Med. Chem. 2009, 52, 5753-5757.
87. Poza, J. J.; Fernandez, R.; Reyes, F.; Rodriguez, J.; Jimenez, C. Isolation, biological significance, synthesis, and cytotoxic evaluation of new natural parathiosteroids A-C and analogues from the soft coral Paragorgia sp. J. Org. Chem. 2008, 73, 7978-7984.
88. Schultz, M. J.; Sigman, M. S. Recent advances in homogeneous transition metal-catalyzed aerobic alcohol oxidations. Tetrahedron 2006, 62, 8227-8241.
89. Matsumoto, T.; Ueno, M.; Wang, N.; Kobayashi, S. Recent Advances in Immobilized Metal Catalysts for Environmentally Benign Oxidation of Alcohols. Chem. Asian J. 2008, 3, 196-214.
90. Kim, S.; Bae, S. W.; Lee, J. S.; Park, J. Recyclable gold nanoparticle catalyst for the aerobic alcohol oxidation and C-C bond forming reaction between primary alcohols and ketones under ambient conditions. Tetrahedron 2009, 65, 1461-1466.
91. Mitsudome, T.; Noujima, A.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Efficient Aerobic Oxidation of Alcohols using a Hydrotalcite-Supported Gold Nanoparticle Catalyst. Adv. Synth. Catal. 2009, 351, 1890-1896.
92. Kwon, M. S.; Kim, N.; Park, C. M.; Lee, J. S.; Kang, K. Y.; Park, J. Palladium Nanoparticles Entrapped in Aluminum Hydroxide: Dual Catalyst for Alkene Hydrogenation and Aerobic Alcohol Oxidation. Org. Lett. 2005, 7, 1077-1079.
93. Mifsud, M.; Parkhomenko, K. V.; Arends, I. W. C. E.; Sheldon, R. A. Pd nanoparticles as catalysts for green and sustainable oxidation of functionalized alcohols in aqueous media. Tetrahedron 2010, 66, 1040-1044.
94. Zaccheria, F.; Ravasio, N.; Psaro, R.; Fusi, A. Synthetic scope of alcohol transfer dehydrogenation catalyzed by Cu/Al2O3: A new metallic catalyst with unusual selectivity. Chem. Eur. J. 2006, 12, 6426-6431.
95. Mitsudome, T.; Mikami, Y.; Ebata, K.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Copper nanoparticles on hydrotalcite as a heterogeneous catalyst for oxidant-free dehydrogenation of alcohols. Chem. Commun. 2008, 4804-4806.
96. Mitsudome, T.; Mikami, Y.; Funai, H.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Oxidant-Free Alcohol Dehydrogenation Using a Reusable HydrotalciteSupported Silver Nanoparticle Catalyst. Angew. Chem. Int. Ed. 2008, 47, 138-141.
97. Lounis, Z.; Riahi, A.; Djafri, F.; Muzart, J. Chromium-exchanged zeolite (CrE-ZSM-5) as catalyst for alcohol oxidation and benzylic oxidation with t-BuOOH. Appl. Catal. A: General 2006, 309, 270-272.
98. He, X.; Chan, T. H. New non-volatile and odorless organosulfur compounds anchored on ionic liquids. Recyclable reagents for Swern oxidation. Tetrahedron 2006, 62, 3389-3394.
99. Uyanik, M.; Ishihara, K. Hypervalent iodine-mediated oxidation of alcohols. Chem. Commun. 2009, 2086-2099.
100. 3-Catalyzed oxidation of alcohols with iodosylbenzene mediated by TEMPO. Synlett 2006, 2055-2058.
101. Telvekar, V. N.; Herlekar, O. P. Mild and Recyclable Hypervalent Iodine System for Oxidation of Alcohols. Synth. Commun. 2007, 37, 859-863.
102. Lapitskaya, M. A.; Vasiljeva, L. L.; Pivnitsky, K. K. o-Iodoxybenzoic acid in dimethylformamide as a convenient reagent for the oxidation of alcohols to aldehydes and ketones. Mendeleev Commun. 2008, 18, 309-311.
103. Linden, J. J. M.; Hilberink, P. W.; Kronenburg, C. M. P.; Kemperman, G. J. Investigation of the Moffatt-Swern Oxidation in a Continuous Flow Microreactor System. Org. Process Res. Dev. 2008, 12, 911-920.
104. 0 Systems. Chem. Eur. J. 2010, 16, 6857-6860.
105. Ciriminna, R.; Pagliaro, M. Industrial Oxidations with Organocatalyst TEMPO and Its Derivatives. Org. Process Res. Dev. 2009, 14, 245-251 and references cited therein.
106. 6]brassinosteroids from 23,24-bisnorcholenic acid methyl ester. Steroids 2004, 69, 617-628.
107. Khripach, V.; Zhabinskii, V. Labeled brassinosteroids for biochemical studies. Chem. Rec. 2007, 7, 265-274.
108. Matsuya, Y.; Masuda, S.; Ohsawa, N.; Adam, S.; Tschamber, T.; Eustache, J.; Kamoshita, K.; Sukenaga, Y.; Nemoto, H. Synthesis and Antitumor Activity of the Estrane Analogue of OSW-1. Eur. J. Org. Chem. 2005, 803-808.
109. Nonappa; Maitra, U. First chemical synthesis, aggregation behavior and cholesterol solubilization properties of pythocholic acid and 16α-hydroxycholic acid. Eur. J. Org. Chem. 2007, 3331-3336.
110. Mukhopadhyay, S.; Maitra, U. Facile synthesis, aggregation behavior, and cholesterol solubilization ability of avicholic acid. Org. Lett. 2004, 6, 31-34.
111. Cravotto, G.; Boffa, L.; Turello, M.; Parenti, M.; Barge, A. Chemical modifications of bile acids under high-intensity ultrasound or microwave irradiation. Steroids 2005, 70, 77-83.
112. Wang, W.; Lee, J.-S.; Nakazawa, T.; Ukai, K.; Mangindaan, R. E. P.; Wewengkang, D. S.; Rotinsulu, H.; Kobayashi, H.; Tsukamoto, S.; Namikoshi, M. (25S)-Cholesten-26-oic acid derivatives from an Indonesian soft coral Minabea sp. Steroids 2009, 74, 758-760.
113. Martin, R.; Entchev, E. V.; Kurzchalia, T. V.; Knolker, H.-J. Steroid hormones controlling the life cycle of the nematode Caenorhabditis elegans: stereoselective synthesis and biology. Org. Biomol. Chem. 2010, 8, 739-750.
114. Martin, R.; Schmidt, A. W.; Theumer, G.; Krause, T.; Entchev, E. V.; Kurzchalia, T. V.; Knolker, H. J. Synthesis and biological activity of the (25R)-cholesten-26-oic acids-ligands for the hormonal receptor DAF-12 in Caenorhabditis elegans. Org. Biomol. Chem. 2009, 909-920.
115. Martin, R.; Entchev, E. V.; Dabritz, F.; Kurzchalia, T. V.; Knolker, H. J. Synthesis and hormonal activity of the (25S)-cholesten-26-oic acids-potent ligands for the DAF-12 receptor in Caenorhabditis elegans. Eur. J. Org. Chem. 2009, 3703-3714.
116. Khripach, V. A.; Zhabinskii, V. N.; Konstantinova, O. V.; Khripach, N. B.; Antonchick, A. V.; Antonchick, A. P.; Schneider, B. Preparation of (25R)-and (25S)-26-functionalized steroids as tools for biosynthetic studies of cholic acids. Steroids 2005, 70, 551-562.
117. Shawakfeh, K. Q.; Al-Said, N. H.; Al-Zoubi, R. M. Synthesis of bisdiosgenin pyrazine dimers: New cephalostatin analogs. Steroids 2008, 73, 579-584.
118. 2O: Simple Oxidation of Alcohols in Solution and Solvent free Conditions. Lett. Org. Chem. 2005, 2, 544-546.
119. Patel, S.; Mishra, B. K. Oxidation of Cholesterol by a Biomimetic Oxidant, Cetyltrimethylammonium Dichromate. J. Org. Chem. 2006, 71, 3522-3526.
120. Aydin, F.; Ozen, R. 3-Carboxypyridinium trifluoroacetatochromate and 3-carboxypyridinium trifluoroacetatochromate, two new and efficient reegents for the oxidation of alcohols, benzylic hydrocarbons and polycyclic aromatic compounds. Org. Prep. Proc. Int. 2007, 39, 616-620.
121. Karade, N. N.; Tiwari, G. B.; Huple, D. B. Molecular Iodine as Efficient Co-Catalyst for Facile Oxidation of Alcohols with Hypervalent(III) Iodine. Synlett 2005, 13, 2039-2042.
122. 2: efficient oxidation of alcohols and trimethylsilyl and tetrahydropyranyl ethers. Lett. Org. Chem. 2006, 3, 292-296.
123. Ozen, R.; Kus, N. S. Oxidation of Alcohols to Carbonyl Compounds, Benzylic Carbons to their Ketones, and Arenes to their Quinones with Molecular Oxygen in Subcritical Water. Monatsh. Chem. 2006, 137, 1597-1600.
124. Bhati, N.; Sarma, K.; Goswami, A. Expedient Method for Oxidation of Alcohol by Hydrogen Peroxide in the Presence of Amberlite IRA 400 Resin (Basic) as Phase-Transfer Catalyst. Synth. Commun. 2008, 38, 1416-1424.
125. Coleman, M. G.; Brown, A. N.; Bolton, B. A.; Guan, H. Iron-Catalyzed Oppenauer-Type Oxidation of Alcohols. Adv. Synth. Catal. 2010, 352, 967-970.
126. Reese, P. B. Remote functionalization reactions in steroids. Steroids 2001, 66, 481-497 and references cited therein.
127. Shul'pin, G. B. Selectivity enhancement in functionalization of C-H bonds: A review. Org. Biomol. Chem. 2010, 8, 4217-4228 and references cited therein.
128. Breslow, R. Biomimetic Chemistry and Artificial Enzymes-Catalysis by Design. Acc. Chem. Res. 1995, 28, 146-153.
129. Breslow, R. Biomimetic Regioselective Template-Directed Functionalizations: An Update. Chemtracts-Org. Chem. 2002, 15, 59-68.
130. Gong, H.; Williams, J. R. Synthesis of the aglycone of the shark repellent pavoninin-4 using remote functionalization. Org. Lett. 2006, 8, 2253-2255.
131. Schönecker, B.; Lange, C. Steroids as chiral model compounds for selective reactions with metals. J. Organomet. Chem. 2006, 691, 2107-2124 and references cited therein.
132. Zhdankin, V. V. Benziodoxole-Based Hypervalent Iodine Reagents in Organic Synthesis. Curr. Org. Synth. 2005, 2, 121-145.
133. Matveeva, E. D.; Proskurnina, M. V.; Zefirov, N. S. Polyvalent iodine in organic chemistry: Recent developments, 2002-2005. Heteroatom Chem. 2006, 17, 595-617.
134. Ladziata, U.; Zhdankin, V. V. Hypervalent iodine(V) reagents in organic synthesis. ARKIVOC 2006, ix, 26-58.
135. Edelsztein, V. C.; Burton, G.; Di Chenna, P. H. Self-assembly of a silylated steroid-based organogelator and its use as template for the in situ sol-gel polymerization of tetraethyl orthosilicate. Tetrahedron 2010, 66, 2162-2167 and references cited therein.
136. Costa, S. C. P.; Moreno, M.; Melo, M.; Neves, A. S. C. Ultrasound assisted remote functionalization of non-activated carbon atoms: efficient in situ formation of tetrahydrofurans by sonolysis of bromohydrins with (diacetoxyiodo) benzene/I2. Tetrahedron Lett. 1999, 40, 8711-8714.
137. Veleiro, A. S.; Taich, P. J.; Alvarez, L. D.; Di Chenna, P. H.; Burton, G. Synthesis of C(1)-C(11) oxygen-bridged pregnanes. Tetrahedron Lett. 2005, 46, 4235-4238.
138. Alvarez, L. D.; Veleiro, A. S.; Baggio, R. F.; Garland, M. T.; Edelsztein, V. C.; Coirini, H.; Burton, G. Synthesis and GABAA receptor activity of oxygen-bridged neurosteroid analogs. Bioorg. Med. Chem. 2008, 16, 3831-3838.
139. Kazakov, V. P.; Voloshin, A. I.; Kazakov, D. V. Dioxiranes: from oxidative transformations to chemiluminescence Russ. Chem. Rev. 1999, 68, 253-286.
140. Iida, T.; Yamaguchi, T.; Nakamori, R.; Hikosaka, M.; Mano, N.; Goto, J.; Nambara, T. A highly efficient, stereoselective oxyfunctionalization of unactivated carbons in steroids with dimethyldioxirane. J. Chem. Soc. Perkin Trans 1 2001, 2229-2236.
141. Iida, T.; Shiraishi, K.; Ogawa, S.; Goto, T.; Mano, N.; Goto, J.; Nambara, T. Functionalization of unactivated carbons in 3α,6-and 3α,24-dihydroxy-5 beta-cholane derivatives by dimethyidioxirane. Lipids 2003, 38, 281-287.
142. Kakiyama, G.; Iida, T.; Goto, T.; Mano, N.; Goto, J.; Nambara, T. Synthesis of 3α,7α,14α-Trihydroxy-5β-cholan-24-oic Acid: A Potential Primary Bile Acid in Vertebrates. Chem. Pharm. Bull. 2004, 52, 371-374.
143. Iida, T.; Hikosaka, M.; Kakiyama, G.; Shiraishi, K.; Schteingart, C. D.; Hagey, L. R.; Ton-Nu, H.-T.; Hofmann, A. F.; Mano, N.; Goto, J.; Nambara, T. Potential Bile Acid Metabolites. 25. Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16-and 3α,7α-15-Trihydroxy-5β-cholan-24-oic Acids. Chem. Pharm. Bull. 2002, 50, 1327-1334.
144. D'Accolti, L.; Fusco, C.; Lampignano, G.; Capitelli, F.; Curci, R. Oxidation of natural targets by dioxiranes. Part 6: on the direct regio-and site-selective oxyfunctionalization of estrone and of 5α-androstane steroid derivatives. Tetrahedron Lett. 2008, 49, 5614-5617 and references cited therein.
145. Ogawa, S.; Kakiyama, G.; Muto, A.; Hosoda, A.; Mitamura, K.; Ikegawa, S.; Hofmann, A. F.; Iida, T. A facile synthesis of C-24 and C-25 oxysterols by in situ generated ethyl(trifluoromethyl)dioxirane. Steroids 2009, 74, 81-87.
146. Wong, M.-K.; Chung, N.-W.; He, L.; Wang, X.-C.; Yan, Z.; Tang, Y.-C.; Yang, D. Investigation on the Regioselectivities of Intramolecular Oxidation of Unactivated C-H Bonds by Dioxiranes Generated in Situ. J. Org. Chem. 2003, 68, 6321-6328.
147. Kasuya, S.; Kamijo, S.; Inoue, M. Direct Construction of 1,3-Diaxial Diol Derivatives by C-H Hydroxylation. Org. Lett. 2009, 11, 3630-3632.
148. Iida, T.; Ogawa, S.; Hosoi, K.; Makino, M.; Fujimoto, Y.; Goto, T.; Mano, N.; Goto, J.; Hofmann, A. F. Regioselective oxyfunctionalization of unactivated carbons in steroids by a model of cytochrome P-450: Osmiumporphyrin complex/tert-butyl hydroperoxide system. J. Org. Chem. 2007, 72, 823-830.
149. Ogawa, S.; Hosoi, K.; Iida, T.; Wakatsuki, Y.; Makino, M.; Fujimoto, Y.; Hofmann, A. F. Osmiumporphyrin-catalyzed oxyfunctionalization and isomerization of natural 5β-bile acids with tert-Butyl hydroperoxide. Eur. J. Org. Chem. 2007, 3555-3563.
150. Fang, Z.; Breslow, R. A thiolate ligand on a cytochrome P-450 mimic permits the use of simple environmentally benign oxidants for biomimetic steroid hydroxylation in water. Bioorg. Med. Chem. Lett. 2005, 15, 5463-5466.
151. Fang, Z.; Breslow, R. Metal Coordination-Directed Hydroxylation of Steroids with a Novel Artificial P-450 Catalyst. Org. Lett. 2005, 8, 251-254.
152. Français, A.; Bedel, O.; Haudrechy, A. Is osmylation always preferring the richest double bond? Tetrahedron 2008, 64, 2495-2524.
153. Zaitsev, A. B.; Adolfsson, H. Recent developments in asymmetric dihydroxylations. Synthesis 2006, 1725-1756 and references cited therein.
154. Samanta, S.; Laha, S. C.; Mal, N. K.; Bhaumik, A. Co(III)-containing mesoporous silica as an efficient catalyst in selective dihydroxylation of cyclohexene. J. Mol. Catal. A 2004, 222, 235-241.
155. Biradar, A. V.; Sathe, B. R.; Umbarkar, S. B.; Dongare, M. K. Selective cisdihydroxylation of olefins using recyclable homogeneous molybdenum acetylide catalyst. J. Mol. Catal. A 2008, 285, 111-119.
156. Wang, A.; Jiang, H. Palladium-Catalyzed Direct Oxidation of Alkenes with Molecular Oxygen: General and Practical Methods for the Preparation of 1,2-Diols, Aldehydes, and Ketones. J. Org. Chem. 2010, 75, 2321-2326.
157. Bathori, M.; Pongracz, Z. Phytoecdysteroids-From isolation to their effects on humans. Curr. Med. Chem. 2005, 12, 153-172.
158. Castilla, V.; Ramírez, J.; Coto, C. E. Plant and Animal Steroids a New Hope to Search for Antiviral Agents. Curr. Med. Chem. 2010, 17, 1858-1873.
159. Misharin, A. Y.; Mehtiev, A. R.; Zhabinskii, V. N.; Khripach, V. A.; Timofeev, V. P.; Tkachev, Y. V. Toxicity of (22R,23R)-22,23-dihydroxystigmastane derivatives to cultured cancer cells. Steroids 2010, 75, 287-294.
160. Khripach, V. A.; Zhabinskii, V. N.; Gulyakevich, O. V.; Konstantinova, O. V.; Misharin, A. Y.; Mekhtiev, A. R.; P, T. V.; Tkachev, Y. V. Synthesis of secasterol and 24-episecasterol and their toxicity for MCF-7 cells Russ. J. Bioorg. Chem. 2010, 36, 746-754.
161. Kovganko, N. V.; Kashkan, Z. N.; Chernov, Y. G.; Ananich, S. K.; Sokolov, S. N.; Survilo, V. L. Synthesis of Ecdysteroids and Related Compounds. Chem. Nat. Compd. 2003, 39, 411-437.
162. Kovganko, N. V.; Ananich, S. K. Progress in the chemical synthesis of brassinosteroids. Chem. Nat. Compd. 2002, 38, 122-141.
163. Kumpun, S.; Yingyongnarongkul, B.-E.; Lafont, R.; Girault, J.-P.; Suksamrarn, A. Stereoselective synthesis and moulting activity of integristerone A and analogues. Tetrahedron 2007, 63, 1093-1099.
164. Homvisasevongsa, S.; Chuaynugul, A.; Chimnoi, N.; Suksamrarn, A. Stereoselective synthesis and moulting activity of 2,3-diepi-20-hydroxyecdysone and 2,3-diepi-5α-20-hydroxyecdysone. Tetrahedron 2004, 60, 3433-3438.
165. Watanabe, B.; Nakagawa, Y.; Ogura, T.; Miyagawa, H. Stereoselective synthesis of (22R)-and (22S)-castasterone/ponasterone A hybrid compounds and evaluation of their molting hormone activity. Steroids 2004, 69, 483-493.
166. Poza, J.; Rega, M.; Paz, V.; Alonso, B.; Rodriguez, J.; Salvador, N.; Fernandez, A.; Jimenez, C. Synthesis and evaluation of new 6-hydroximinosteroid analogs as cytotoxic agents. Bioorg. Med. Chem. 2007, 15, 4722-4740.
167. Milic, D.; Kop, T.; Juranic, Z.; Gasic, M. J.; Tinant, B.; Pocsfalvi, G.; Solaja, B. A. Synthesis and antiproliferative activity of A-ring aromatised and conduritol-like steroidal compounds. Steroids 2005, 70, 922-932.
168. Michelini, F. M.; Ramírez, J. A.; Berra, A.; Galagovsky, L. R.; Alché, L. E. Anti-herpetic and anti-inflammatory activities of two new synthetic 22,23-dihydroxylated stigmastane derivatives. J. Steroid Biochem. Mol. Biol. 2008, 111, 111-116.
169. Michelini, F. M.; Ramírez, J. A.; Berra, A.; Galagovsky, L. R.; Alché, L. E. In vitro and in vivo antiherpetic activity of three new synthetic brassinosteroid analogues. Steroids 2004, 69, 713-720.
170. Ramírez, J. A.; Bruttomesso, A. C.; Michelini, F. M.; Acebedo, S. L.; Alché, L. E.; Galagovsky, L. R. Syntheses of immunomodulating androstanes and stigmastanes: Comparison of their TNF-α inhibitory activity. Bioorg. Med. Chem. 2007, 15, 7538-7544.
171. Romero-Avila, M.; de Dios-Bravo, G.; Mendez-Stivalet, J. M.; Rodríguez-Sotres, R.; Iglesias-Arteaga, M. A. Synthesis and biological activity of furostanic analogues of brassinosteroids bearing the 5α-hydroxy-6-oxo moiety. Steroids 2007, 72, 955-959.
172. Yamamoto, S.; Watanabe, B.; Otsuki, J.; Nakagawa, Y.; Akamatsu, M.; Miyagawa, H. Synthesis of 26,27-bisnorcastasterone analogs and analysis of conformation-activity relationship for brassinolide-like activity. Bioorg. Med. Chem. 2006, 14, 1761-1770.
173. Litvinovskaya, R.; Raiman, M.; Khripach, V. Synthesis of 22-and 23-oxoderivatives of 28-homocastasterone. Russ. J. Org. Chem. 2008, 44, 1614-1618.
174. Khripach, V. A.; Zhabinskii, V. N.; Ermolovich, Y. V. Improved Synthesis of 28-Norbrassinolide Synth. Commun. 2010, 40, 2780-2787.
175. Litvinovskaya, R.; Raiman, M.; Khripach, V. Synthesis of 28-homobrassinosteroids modified in the 26-position. Chem. Nat. Compd. 2009, 45, 647-652.
176. Alivert, A.; Brosa, C.; Canals, F.; Malet, C. Synthesis and activity evaluation of new 11α-hydroxybrassinosteroids. Afinidad LXIV 2007, 216-224.
177. Litvinovskaya, R.; Baranovsky, A.; Averkova, M.; Khripach, V. The synthesis of 2α,3α-isopropylidenedioxy-6,6-ethylenedioxy-5α-androst-15-en-17-one and its 2β,3β-isomer. Russ. J. Bioorg. Chem. 2007, 33, 320-325.
178. Slavikova, B.; Kohout, L.; Budesinsky, M.; Swaczynova, J.; Kasal, A. Brassinosteroids: Synthesis and Activity of Some Fluoro Analogues. J. Med. Chem. 2008, 51, 3979-3984.
179. Deive, N.; Rodriguez, J.; Jimenez, C. Synthesis of cytotoxic 6Ehydroximino-4-ene steroids: Structure/activity studies. J. Med. Chem. 2001, 44, 2612-2618.
180. Rivera, D. G.; Leon, F.; Coll, F.; Davison, G. P. Novel 5β-hydroxyspirostan-6-ones ecdysteroid antagonists: Synthesis and biological testing. Steroids 2006, 71, 1-11.
181. Marino, J. P.; de Dios, A.; Anna, L. J.; de la Pradilla, R. F. Highly stereocontrolled formal synthesis of brassinolide via chiral sulfoxide-directed S(N)2' reactions. J. Org. Chem. 1996, 61, 109-117 and references cited therein.
182. Litvinovskaya, R.; Aver'kova, M.; Baranovskii, A.; Khripach, V. Synthesis of 6-deoxo-24-epiteasterone and its analogs. Russ. J. Org. Chem. 2006, 42, 1325-1332.
183. Xue, J.; Liu, P.; Pan, Y.; Guo, Z. A Total Synthesis of OSW-1. J. Org. Chem. 2008, 73, 157-161.
184. Shull, B. K.; Koreeda, M. Reduction of 17α-hydroxy-20-keto steroids: convenient synthesis of (E)-3β-hydroxy-5,17(20)-pregnadiene 3-pivaloate and (Z)-3β,16α-dihydroxy-5,17(20)-pregnadiene 3-pivaloate. J. Org. Chem. 1990, 55, 99-105.
185. Tsubuki, M.; Matsuo, S.; Honda, T. A new synthesis of potent antitumor saponin OSW-1 via Wittig rearrangement. Tetrahedron Lett. 2008, 49, 229-232.
186. Chen, L.-J.; Xu, Q.-H.; Huang, H.; Lin, J.-R.; Tian, W.-S. Synthesis of 5(6)-dihydro-OSW-1 by using the intact skeleton of tigogenin. Tetrahedron Lett. 2007, 48, 3475-3477.
187. Lee, S.; LaCour, T. G.; Fuchs, P. L. Chemistry of Trisdecacyclic Pyrazine Antineoplastics: The Cephalostatins and Ritterazines. Chem. Rev. 2009, 109, 2275-2314.
188. Moser, B. R. Review of Cytotoxic Cephalostatins and Ritterazines: Isolation and Synthesis. J. Nat. Prod. 2008, 71, 487-491.
189. Gryszkiewicz-Wojtkielewicz, A.; Jastrzebska, I.; Morzycki, J. W.; Romanowska, D. B. Approaches Towards the Synthesis of Cephalostatins, Ritterazines and Saponins from Ornithogalum saundersiae - New Natural Products With Cytostatic Activity Curr. Org. Chem. 2003, 12, 1257-1277.
190. Lee, S.; Jamieson, D.; Fuchs, P. L. Synthesis of C14,15-Dihydro-C22,25-epi North Unit of Cephalostatin 1 via "Red-Ox" Modifications of Hecogenin Acetate. Org. Lett. 2009, 11, 5-8.