Olefin cross-metathesis as a tool in natural product degradation. The stereochemistry of (+)-falcarindiol.
[reaction: see text] There are conflicting reports in the literature concerning the absolute sterochemistry at C-3 of the common plant polyacetylene oxylipin (+)-falcarindiol. We have employed olefin cross-metathesis using Grubbs' second generation catalyst and ethylene gas to degrade falcarindiol to the symmetrical 1,9-decadiene-4,6-diyne-3,8-diol. The reaction is completely selective for net removal of the aliphatic side chain. Degradation of (+)-falcarindiol from Tetraplasandra hawaiiensis yields a meso product as shown by chiral HPLC. Hence, (+)-falcarindiol from this source has a (3R,8S)-configuration.
Ratnayake
Anokha S
AS
Department of Chemistry, University of Hawaii, 2545 McCarthy Mall, Honolulu, Hawaii 96822, USA.
Hemscheidt
Thomas
T
D000475:Alkenes / Q000737:chemistry; D000970:Antineoplastic Agents / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D053280:Diynes; D005233:Fatty Alcohols / Q000737:chemistry*; D015394:Molecular Structure; D009904:Optical Rotation; D013237:Stereoisomerism
D000475:Alkenes; D000970:Antineoplastic Agents; D053280:Diynes; D005233:Fatty Alcohols; C034379:falcarindiol