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.
Inhalt
Preface
Abbreviations
1. Designing Total Syntheses
1.1 Introduction
1.2 Defining the Problem
1.3 Methods and Reactions
1.4 Resolutions
References
2. Biogenetic-like Steroid Synthesis
2.1 Cyclization of Terminal Epoxides
2.2 Total Synthesis from Nonepoxide Precursors
References
3. 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
References
4. 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
References
5. AB + D ABCD
5.1 Introduction
5.2 Carbocyclics
5.3 Thiasteroids
References
6. A + C AC ABC ABCD
6.1 Synthesis from p-Anisylcyclohexanes
6.2 Synthesis from C-5,C-8 Bridged Intermediates
References
7. 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
References
8. A + D AD ABCD
8.1 The Smith-Hughes Approach
8.2 8-Azasteroids
8.3 8,13-Diazasteroids
8.4 Miscellaneous Routes
References
9. 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
References
10. 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
References
11. B + D BD BCD ABCD
Discussion
References
12. 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
References
Appendix. Supplementary References
Author Index
Subject Index