Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Regioselective and enantioselective addition of thioacids to terminal allenes is reported employing a rhodium(i)/DIOP catalyst system. Complete catalyst control of diastereoselectivity was achieved upon addition of chiral amino thioacids to allenes.

Catalytic Enantioselective Addition of Alkylzirconium Reagents to Aliphatic Aldehydes

A catalytic methodology for the enantioselective addition of alkylzirconium reagents to aliphatic aldehydes is reported here. The versatile and readily accessible chiral Ph-BINMOL ligand, in the presence of Ti(OiPr)4 and a zinc salt, facilitates the reaction, which proceeds under mild conditions and is compatible with functionalized nucleophiles. The alkylzirconium reagents are conveniently generated in situ by hydrozirconation of alkenes with the Schwartz reagent. This work is a continuation of our previous work on aromatic aldehydes.