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, 3β-hydroxy-5α-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.

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 3β-Hydroxy-5α-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 7α-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