Stable P-stereogenic P(Ⅲ)fluorides of the type*PR^(1)R^(2)F have long resisted isolation,despite their great potential as ligands in asymmetric catalysis.We report the synthesis of a crystalline,chiral lithium alkene...Stable P-stereogenic P(Ⅲ)fluorides of the type*PR^(1)R^(2)F have long resisted isolation,despite their great potential as ligands in asymmetric catalysis.We report the synthesis of a crystalline,chiral lithium alkenephosphide that undergoes rapid,enantiospecific fluorination with N-fluorobenzenesulfonimide with retention of configuration to yield the corresponding fluorophosphinamide–alkene hybrid ligand in>99%ee.The ligand is configurationally stable up to 100℃ and forms a Rh(I)complex that catalyzes the base-and waterfree asymmetric arylation of isatins to biologically important 3-hydroxyoxindoles with up to 99.5%ee.展开更多
基金the elemental analyses,Mr Shao Kai Lu for assistance in up-scaling the synthesis of(pR,SP)-7,and Mr Jochen Schmidt for measuring NMR spectraFinancial support by Friedrich-Alexander University is gratefully acknowledged.
文摘Stable P-stereogenic P(Ⅲ)fluorides of the type*PR^(1)R^(2)F have long resisted isolation,despite their great potential as ligands in asymmetric catalysis.We report the synthesis of a crystalline,chiral lithium alkenephosphide that undergoes rapid,enantiospecific fluorination with N-fluorobenzenesulfonimide with retention of configuration to yield the corresponding fluorophosphinamide–alkene hybrid ligand in>99%ee.The ligand is configurationally stable up to 100℃ and forms a Rh(I)complex that catalyzes the base-and waterfree asymmetric arylation of isatins to biologically important 3-hydroxyoxindoles with up to 99.5%ee.
