Intramolecular silicon-assisted cross-coupling: total synthesis of (+)-brasilenyne.
The first, total synthesis of (+)-brasilenyne (1) has been achieved in 19 steps from l-(S)-malic acid. The key elements of this approach are a highly diastereoselective ring-opening of a 1,3-dioxolanone with bis(trimethylsilyl)acetylene) promoted by TiCl4 to set a propargylic stereocenter and the successful application of the sequential ring closing metathesis/silicon-assisted intramolecular cross-coupling reaction for construction of the oxonin core structure of 1.
Denmark
Scott E
SE
Roger Adams Laboratory, Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA. denmark@scs.uiuc.edu
Yang
Shyh-Ming
SM
D000818:Animals; D001048:Aplysia / Q000737:chemistry; D004988:Ethers, Cyclic / Q000138:chemical synthesis*; D012825:Silicon / Q000737:chemistry*; D013237:Stereoisomerism
D004988:Ethers, Cyclic; C471861:brasilenyne; D012825:Silicon