Enantioselective catalysis of intramolecular Morita-Baylis-Hillman and related reactions by chiral rhenium-containing phosphines of the formula (eta(5)-C5H5)Re(NO)(PPh3)(CH2PAr2)
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The racemic rhenium-containing phosphine (5-C 5H5)Re(NO)(PPh3)(CH2PPh 2) catalyzes intramolecular Morita-Baylis-Hillman reactions of four R(CO)CH=CH(CH2)nCH2CHO species (n = 1 or 2; R = Ph, S-i-Pr, p-Tol, Me) in benzene or chlorobenzene at 20C. The products R(CO)CH=CH(CH2)nCH2CHOH are isolated in 88-99% yields and 38-74% ee when enantiopure S-configured catalyst is used. Similar reactions of R(CO)CH=CHCH2CH2CH=CH(CO)R (R = Ph, S-i-Pr) give R(CO)C=CHCH2CH2CHCH2(CO)R in 63-87% yields and 42-56% ee. Georg Thieme Verlag Stuttgart.