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[摘要]：TADDOL-derived phosphites and phosphoramidites are effective ligands for rhodium-catalyzed asymmetric hydroborations of beta,gamma-unsaturated amides, achieving up to 99% ee. However, the sense of stereoinduction, R or S, is surprisingly dependent on rather subtle features of the ligand. For example, catalysts employing a TADDOL phenylphosphite and those using the closely related N-methylaniline-derived phosphoramidite of the same configuration give opposite enantiomers of the product. Those derived from optical antipodes give the same product with virtually the same enantioselectivity as illustrated above The different stereochemical outcomes may reflect fundamental differences in catalyst structure, reactivity, or reaction mechanism. |
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