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Diastereoselective rhodium(II)-catalyzed sulfonium ylide formation-[2,3]-sigmatropic rearrangement reaction of chiral non-racemic allylic sulfides

✍ Scribed by Andrew G.H Wee; Qing Shi; Zhongyi Wang; Kimberly Hatton

Publisher: Elsevier Science
Year: 2003
Tongue: English
Weight: 240 KB
Volume: 14
Category: Article
ISSN: 0957-4166
DOI: 10.1016/s0957-4166(03)00079-x

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✦ Synopsis

The tandem sulfonium ylide formation-[2,3]-sigmatropic rearrangement reaction of chiral non-racemic secondary allylic sulfides, (E)-9 and (Z)-10, is found to proceed with high diastereocontrol. The C-5 stereocenter bearing the sulfide group is essential for high diastereoselectivity in the reaction. Transition state conformers are proposed to explain the high diastereoselectivity in the formation of the diastereomeric products, 18a and 18b. The method is applied to the synthesis of (R)-4-(4chlorophenyl)-2-butyrolactone. Modest enantioselectivity (63% ee) was achieved and this is attributed to partial racemization during the formation of the secondary allylic sulfide 22.

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