Synthesis and application of modular phosphine-phosphoramidite ligands in asymmetric hydroformylation: structure-selectivity relationship.

Abstract

A series of hybrid phosphine-phosphoramidite ligands has been designed and synthesized in moderate yields from chiral BINOL (1,1'-bi-2-naphthol) or NOBIN (2-amino-2'-hydroxy-1,1'-binaphthyl). They have achieved highly regio- and enantioselectivities in Rh-catalyzed asymmetric hydroformylations of styrene derivatives (branched/linear ratio up to 56.6, ee up to 99 %), vinyl acetate derivatives (up to 98 % ee), and allyl cyanide (up to 96 % ee). Systematic variation of ligand structure showed that the steric factor on the phsophoramidite moiety determined the performance of the ligand. With the increased hindrance, the branched/linear ratio rose, while the ee value dropped in the hydroformylation of styrene. However, the N-substituents did not influence the selectivities much.

DOI: 10.1002/chem.200902238

Cite this paper

@article{Zhang2010SynthesisAA, title={Synthesis and application of modular phosphine-phosphoramidite ligands in asymmetric hydroformylation: structure-selectivity relationship.}, author={Xiaowei Zhang and Bonan Cao and Yongjun Yan and Shichao Yu and Baoming Ji and Xumu Zhang}, journal={Chemistry}, year={2010}, volume={16 3}, pages={871-7} }