期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 -, 期 -, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202303853
关键词
1; 3-Dienes; Hemilabile Ligand; Hydrosilylation; P; O Ligand; Regioselective Catalysis
Novel P, O-type ligands, N-disulfonyl bicyclic bridgehead phosphorus triamides, exhibited high reactivity in Pd-catalyzed hydrosilylation reactions involving tertiary silanes, unactivated alkenes, and conjugated dienes. The use of these ligands significantly improved the regioselectivity of diene hydrosilylation towards 1,2-hydrosilylation. Experimental and computational studies confirmed the bidentate nature of the ligand and provided insights into the reaction mechanism.
Novel P,O-type ligands, N-disulfonyl bicyclic bridgehead phosphorus triamides, were synthesized and utilized in Pd-catalyzed hydrosilylation involving tertiary silanes, unactivated alkenes, and conjugated dienes. The ligand displayed a remarkable level of reactivity for alkene hydrosilylation with tertiary silanes and its use resulted in a significant improvement in the regioselectivity of diene hydrosilylation towards 1,2-hydrosilylation. X-ray crystallographic analysis confirmed the bidentate nature of the ligand, with coordination of phosphorus and oxygen. Control experiments provided evidence for the formation of Pd-0 species and the reversibility of Pd-H insertion in the reaction mechanism. Density functional theory (DFT) computations supported the importance of the hemilabile P,O ligand in stabilizing both the rate-determining transition state of Pd-H insertion and the transition state of reductive elimination that determines the regioselectivity.
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