Abstract

AbstractA simple, broad‐scope rhodium(I)/chiral diene catalytic system for challenging asymmetric intramolecular cyclopropanation of various tri‐substituted allylic diazoacetates was successfully developed. The low coordination state RhI‐complex exhibits an extraordinarily high degree of tolerance to the variation in the extent of substitution of the allyl double bond, thus allowing the efficient construction of a wide range of penta‐substituted, fused‐ring cyclopropanes bearing three contiguous stereogenic centers, including two quaternary carbon stereocenters, in a highly enantioselective manner with ease at catalyst loading as low as 0.1 mol %. The stereoinduction mode of this RhI‐carbene‐directed asymmetric intramolecular cyclopropanation was investigated by DFT calculations, indicating that π‐π stacking interactions between the aromatic rings of chiral diene ligand and diazo substrate play a key role in the control of the reaction enantioselectivity.

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