期刊
ACS CATALYSIS
卷 6, 期 6, 页码 3955-3964出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.6b00784
关键词
P,N-ligands; QUINAP; DYKAT; asymmetric catalysis; C-P coupling; silylphosphines; heterobiaryls
资金
- ERDF
- ESF
- FP7 (ITN ECHONET network) [MCITN-2012-316379]
- Ministerio de Economia y Competitividad [CTQ2013-48164-C2-1-P, CTQ2013-48164-C2-2-P, RYC-2013-12585]
- Junta de Andalucia [2012/FQM 1078]
The Pd-catalyzed enantioselective C-P cross coupling between racemic, configurationally stable heterobiaryl triflates and trialkylsilyldiaryl(dialkyl)phosphines has been used for the synthesis of several families of enantiomerically enriched heterobiaryl phosphines including QUINAP, PINAP, and QUINAZOLINAP analogues, which can be performed with good yields and enantioselectivities using JOSIPHOS-type bidentate phosphines. The strategy relies on two key assumptions: (I) The N atom of the heterocycle is a better ligand than triflate, and upon oxidative addition, it incorporates into the coordination sphere of the Pdil center to form cationic cyclic intermediates. (II) The geometry of the palladacycle results in a widening of the angles involved in the stabilization of the stereogenic axis, facilitating a fast interconversion of diastereomeric structures and, hence, a dynamic kinetic C-P cross-coupling reaction. These starting hypotheses are supported by experimental and computational studies.
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