Total Synthesis of Steroids

Organic Chemistry, Volume 30: Total Synthesis of Steroids provides an overall view of steroid total synthesis, including the general approaches, special problems, stereochemical complexities, expansion or contraction of rings, and insertion of hetero atoms. The book discusses the process of designing total syntheses; the biogenetic-like steroid synthesis, including cyclization of terminal epoxides as well as the total synthesis from nonepoxide precursors; and the synthesis of equilenin, estrone, bisdehydrodoisynolic acid, 18,19-bisnorprogesterone, 19-norpregnanes, and heterocyclic steroids. The text also describes the application of ABD intermediates in the Torgov synthesis; the synthesis of carbocyclics and thiasteroids; and the synthesis from p-anisylcyclohexanes and from C-5, C-8 bridged intermediates. The synthesis based on the type of reaction used in the condensation of the A fragment with the CD portion, as well as the methods of total synthesis in the preparation of 8-azasteroids and 8,13-diazasteroids are also considered. The book further tackles the synthesis of epiandrosterone, cortisone, aldosterone, 3ß-hydroxy-5a-pregnan-20-one, latifoline, conessine, and ring C aromatic steroids; the synthesis of trans-benzohydrindane derivatives and other common derivatives; and the synthesis of CD intermediates. Chemists, biochemists, and people involved in the study of steroid total syntheses will find the book invaluable.

PrefaceAbbreviations1. Designing Total Syntheses 1.1 Introduction 1.2 Defining the Problem 1.3 Methods and Reactions 1.4 Resolutions References2. Biogenetic-like Steroid Synthesis 2.1 Cyclization of Terminal Epoxides 2.2 Total Synthesis from Nonepoxide Precursors References3. AB ¿ ABC ¿ ABCD 3.1 Equilenin 3.2 Estrone 3.3 Bisdehydrodoisynolic Acid 3.4 18,19-Bisnorprogesterone and 19-Norpregnanes 3.5 Miscellaneous Syntheses 3.6 Heterocyclic Steroids References4. AB + D ¿ ABD ¿ ABCD 4.1 Introduction 4.2 The Torgov Synthesis 4.3 Alkylation 4.4 Michael Addition 4.5 Enamines 4.6 Acylation 4.7 Aldol-Type Condensations 4.8 Organometallic Coupling 4.9 Miscellaneous Methods References5. AB + D ¿ ABCD 5.1 Introduction 5.2 Carbocyclics 5.3 Thiasteroids References6. A + C ¿ AC ¿ ABC ¿ ABCD 6.1 Synthesis from p-Anisylcyclohexanes 6.2 Synthesis from C-5,C-8 Bridged Intermediates References7. A + CD ¿ ACD ¿ ABCD 7.1 Condensation of Ring-A Anionic Fragments with CD Ketones 7.2 Alkylation of an Anionic CD Fragment 7.3 The Wittig Reaction in Total Synthesis 7.4 CD Enamine Intermediates 7.5 Thiasteroids 7.6 Miscellaneous Routes References8. A + D ¿ AD ¿ ABCD 8.1 The Smith-Hughes Approach 8.2 8-Azasteroids 8.3 8,13-Diazasteroids 8.4 Miscellaneous Routes References9. BC ¿ ABC ¿ ABCD 9.1 Synthesis of Epiandrosterone 9.2 Other Methods 9.3 Synthesis According to Wilds 9.4 Synthesis of Cortisone 9.5 Synthesis of Aldosterone 9.6 3ß-Hydroxy-5a-pregnan-20-one, Latifoline, and Conessine 9.7 Ring-C Aromatic Steroids References10. BC ¿ BCD ¿ ABCD 10.1 Introduction 10.2 Trans-Benzohydrindane Derivatives 10.3 19-Nortestosterone 10.4 Adrenocortical Steroids 10.5 Estrogens 10.6 10-Allyl Steroids 10.7 19-Norprogesterone and 11-Hydroxysteroids 10.8 Trienes 10.9 7a-Methyl Steroids 10.10 Miscellaneous Steroidal Derivatives 10.11 Isosteroids 10.12 11-Oxygenated Steroids and Conessine 10.13 Miscellaneous Synthetic Routes References11. B + D ¿BD ¿ BCD ¿ ABCD Discussion References12. CD ¿ BCD ¿ ABCD 12.1 CD Intermediates 12.2 Hydrochrysene Approach 12.3 Modification of the Hydrochrysene Synthesis 12.4 C-Nor-D-homosteroids 12.5 Woodward Synthesis 12.6 Asymmetric Induction 12.7 Hoffman-LaRoche Approach 12.8 Miscellaneous Syntheses ReferencesAppendix. Supplementary ReferencesAuthor IndexSubject Index