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Rhodium(I)/bisoxazolinephosphine combination has been developed as a general catalyst to achieve the dynamic kinetic asymmetric allylation of a variety of nitrogen, carbon, oxygen, and sulfur pronucleophiles from branched racemic allylic carbonates. Exclusive branch-selectivity and up to 99% enantiomeric excess could be obtained under neutral conditions. Linear allylic substrates (both Z and E ) could be converted to the same chiral branched products with excellent regio- and enantioselectivities as well. Chiral π-allyl-Rh(III)/NPN intermediate was isolated and characterized to understand the origin of the high selectivities.
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Xu et al. (2020) studied this question.
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