The heteroleptic dirhodium paddlewheel catalyst 7 with a chiral carboxylate/acetamidate ligand sphere is uniquely effective in asymmetric [2+1] cycloadditions with α-diazo-α-trimethylstannyl (silyl, germyl) acetate. Originally discovered as a trace impurity in a sample of the homoleptic parent complex [Rh2 ((R)-TPCP)4 ] (5), it is shown that the protic acetamidate ligand is quintessential for rendering 7 highly enantioselective. The -NH group is thought to lock the ensuing metal carbene in place via interligand hydrogen bonding. The resulting stannylated cyclopropanes undergo "stereoretentive" cross coupling, which shows for the first time that even chiral quarternary carbon centers can be made by the Stille-Migita reaction.
Keywords: Stille coupling; asymmetric catalysis; cyclopropanation; heteroleptic complexes; quarternary chiral centers; rhodium carbenes.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.