The direct aldol-type condensation of aldehydes with ethyl diazoacetate catalyzed by the chiral complex of BINOL derivatives-Zr(O(t)Bu)(4) gave beta-hydroxy alpha-diazo carbonyl compounds with moderate enantioselectivities (53-87% ee). [reaction: see text]

The Rh2(OAc)4‐catalyzed reaction of methyl aryldiazoacetates with thioacetic S‐acid gives exclusively the S−H insertion products in high yields, while the corresponding reaction mediated by BF3·OEt2 gives O‐esters. The mechanism of the reaction is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003

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