Total synthesis of amphilectane-type diterpenoids: (±)-8,15-diisocyano-11(20)-amphilectene

Autor:	Edward Piers, Renata M. Oballa, Montse Llinas-Brunet
Rok vydání:	1993
Předmět:	Stereochemistry Isocyanide Organic Chemistry Acrolein Total synthesis General Chemistry Alkylation Antimicrobial Catalysis Terpenoid chemistry.chemical_compound chemistry Organic chemistry Diterpene
Zdroj:	Canadian Journal of Chemistry. 71:1484-1494
ISSN:	1480-3291 0008-4042
DOI:	10.1139/v93-189
Popis:	A total synthesis of the structurally novel, antimicrobial diterpenoid (±)-8,15-diisocyano-11(20)-amphilectene (2) is described. Alkylation of 2-methoxycarbonyl-3-methylcyclohexanone (13) with (E)-1-(tert-butyldimethylsiloxy)-6-iodo-3-(trimethylstannyl)-2-hexene (14) provided, stereoselectively, the functionalized keto ester 15, which was converted efficiently into the diene 17. Diels–Alder reaction of 17 with acrolein, followed by base-catalyzed equilibration of the resultant product mixture, gave the aldehydes 19 (58%) and 20 (29%). Allylic oxidation of the alkene 24 (derived from 19) afforded the enone 25. Reduction (Na, NH3, t-BuOH) of 25 gave 28, which was converted, via a sequence of eight synthetic steps, into the diacid 45. Efficient transformation of the carboxyl functions of 45 into isonitrile groups completed the synthesis of (±)-2.
Databáze:	OpenAIRE
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