Aziridine−Allylsilane-Mediated Total Synthesis of (−)-Yohimbane
- 1 April 1999
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 64 (9) , 3237-3243
- https://doi.org/10.1021/jo9825097
Abstract
A total asymmetric synthesis of (−)-yohimbane and ent-alloyohimbane is reported. The synthesis utilizes a novel aziridine−allylsilane cyclization reaction as a key step in the synthesis. Treatment of optically pure aziridine−allylsilane 16 with BF3·OEt2 provided a mixture of aminomethyl substituted carbocycles trans-20a and cis-20b in excellent yield and modest diastereoselectivity (trans/cis 3:1). Alkylation of the tosylamide followed by oxidation of the olefin in 20 provided the lactam 38, which was converted to (−)-yohimbane and ent-alloyohimbane by a Bischler−Napieralski reaction. The synthesis provided (−)-yohimbane in eight steps and 24% overall yield (from 16).Keywords
This publication has 38 references indexed in Scilit:
- Symmetry-Driven Synthesis of Indole Alkaloids: Asymmetric Total Syntheses of (+)-Yohimbine, (-)-Yohimbone, (-)-Yohimbane, and (+)-AlloyohimbaneJournal of the American Chemical Society, 1994
- TheMitsunobu ReactionPublished by Wiley ,1992
- Stereoselective additions of chiral .alpha.-sulfinyl ketimine anions to ene esters. Asymmetric syntheses of indolo[2,3-a]quinolizidine and yohimban alkaloidsThe Journal of Organic Chemistry, 1991
- Stereoselective addition reactions of chiral .alpha.-sulfinyl ketimine anions with ene esters. Facile asymmetric synthesis of indolo[2,3-a]quinolizidine and yohimbanoid alkaloidsThe Journal of Organic Chemistry, 1989
- One-step conversion of primary alcohols in the carbohydrate series to the corresponding carboxylic tert-butyl estersThe Journal of Organic Chemistry, 1984
- 2-Alkoxybenzo-1,3-dithiole 1,1,3,3-tetraoxide. A carbonyl 1,1-dipole synthonJournal of the American Chemical Society, 1984
- New methods and reagents in organic synthesis. 14. A simple efficient preparation of methyl esters with trimethylsilyldiazomethane (TMSCHN2) and its application to gas chromatographic analysis of fatty acids.CHEMICAL & PHARMACEUTICAL BULLETIN, 1981
- Cleavage of sulfonamides with sodium naphthaleneJournal of the American Chemical Society, 1967
- THE TOTAL SYNTHESIS OF YOHIMBINEJournal of the American Chemical Society, 1958
- Alkaloids of Banisteria caapi and Prestonia amazonicumJournal of the American Chemical Society, 1957