Title | Synthetic studies toward halichlorine: Complex azaspirocycle formation with use of an NBS-promoted semipinacol reaction |
Publication Type | Journal Article |
Year of Publication | 2008 |
Authors | Hurley, PB, Dake, GR |
Journal | Journal of Organic Chemistry |
Volume | 73 |
Pagination | 4131-4138 |
Date Published | Jun |
Type of Article | Article |
ISBN Number | 0022-3263 |
Keywords | (+/-)-PINNAIC ACID, ASYMMETRIC-SYNTHESIS, BAEYER-VILLIGER OXIDATION, CARBOXYLIC-ACIDS, CRIEGEE REARRANGEMENT, ETHYLMAGNESIUM BROMIDE, ORGANIC-SYNTHESIS, PINNAIC ACID, RING-CLOSING METATHESIS, SPIROCYCLIC CORE |
Abstract | The investigations of a synthetic route incorporating a NIBS-promoted semipinacol rearrangement to the 6-azaspiro[4.5]decane fragment within halichlorine (1) are presented. A convergent approach was pursued, utilizing two chiral, enantiomerically enriched building blocks, 2-trimethylstannyl piperidene 10 and substituted cyclobutanone 19. Noteworthy synthetic operations in this study include the following: (a) a highly diastereoselective NBS-promoted semipinacol reaction that established four stereogenic centers in ketone 25 and (b) the use of a N-p-toluenesulfonyl-2-iodo-2-piperidene as a precursor to a basic organometallic reagent, which was critical to the success of the coupling of fragments 10 and 19. |
URL | <Go to ISI>://000256323500018 |
