jo034533c_si_006.pdf (3.26 MB)
New Strategic Reactions for Organic Synthesis: Catalytic Asymmetric C−H Activation α to Oxygen as a Surrogate to the Aldol Reaction
journal contribution
posted on 2003-07-15, 00:00 authored by Huw M. L. Davies, Rohan E. J. Beckwith, Evan G. Antoulinakis, Qihui JinThe C−H activation of silyl ethers by means of rhodium carbenoid-induced C−H insertion represents
a very direct method for the stereoselective synthesis of silyl-protected β-hydroxy esters. The reaction
can proceed with very high regio-, diastereo-, and enantioselectivity and represents a surrogate to
the aldol reaction. The reaction is catalyzed by the rhodium prolinate complex Rh2(S-DOSP)4. A
critical requirement for the high chemoselectivity is the use of donor/acceptor-substituted carbenoids
such as those derived from methyl aryldiazoacetates. A range of silyl ethers may be used such as
allyl silyl ethers, tetraalkoxysilanes, and even simple trimethylsilyl alkyl ethers. In general, C−H
activation preferentially occurs at methylene sites, as the reactivity is controlled by a delicate balance
between steric and electronic effects.