Chiral‐at‐metal RhIII complexes catalyze the efficient enantioselective Mannich reaction of 2‐acyl imidazoles with 1,3,5‐triazinanes, affording the corresponding adducts in 81–99 % yield with up to >99 % enantioselectivity. This protocol performs with 0.1 mol‐% of RhIII complex on gram scale without any loss in enantioselectivity.
Unlike the comprehensive development of tandem multi-metallic catalysis, bimetallic synergistic catalysis has been challenging to achieve high stereoselectivity with the generation of multi-stereogenic centers. Herein, an efficient synergistic catalysis for the diastereo-and enantioselective synthesis of multi-substituted tetrahydrofuran derivatives has been developed. Under mild reaction conditions, a series of target molecules with three consecutive stereocenters were synthesized by a palladium(0)/ rhodium(III) bimetal-catalyzed asymmetric decarboxylative [3 + 2]-cycloaddition of vinylethylene carbonates with α,βunsaturated carbonyl compounds. The corresponding adducts were obtained with moderate to high yields (67 %9 8 %) and excellent stereoselectivities (> 20 : 1 d.r., up to 99 % ee).
An asymmetric [3+2] cycloaddition of C,N-cyclic azomethine imines with α,β-unsaturated 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium complex has been developed.
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