Ligand Control of the Cobalt-Catalysed 1,4-Hydrovinylation Reaction

被引：25

作者：

Arndt, Marion ^{[1
]}

Dindaroglu, Mehmet ^{[2
]}

Schmalz, Hans-Guenther ^{[2
]}

Hilt, Gerhard ^{[1
]}

机构：

[1] Univ Marburg, Fachbereich Chem, D-35043 Marburg, Germany

[2] Univ Cologne, Dept Chem, D-50939 Cologne, Germany

来源：

SYNTHESIS-STUTTGART | 2012年 / 44卷 / 22期

关键词：

alkene; catalysis; cobalt; diene; 1,4-hydrovinylation; PHOSPHINE-PHOSPHITE-LIGANDS; BIDENTATE CHELATE LIGANDS; ASYMMETRIC HYDROVINYLATION; ALPHA-OLEFINS; ENANTIOSELECTIVE HYDROVINYLATION; MODULAR APPROACH; DIELS-ALDER; STYRENES; 1,4-ADDITION; DIMERIZATION;

D O I：

10.1055/s-0032-1316796

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The application of cobalt catalysts to the hydrovinylation of unsymmetrical alkenes and 1,3-dienes was investigated using modular phosphine-phosphite ligands to evaluate the influence of the ligands on the regioselectivity of the reaction. While a ligand with a TADDOL subunit (SchmalzPhos) gave the best results for the beta-4 regioisomer, the corresponding BINOL-derived ligand gave predominantly the beta-1 regioisomer. The application of (E)-2-methylpenta-1,3-diene in combination with the (nonracemic) BINOL-derived ligand generated the beta-4 regioisomer in excellent yields and very high regioselectivities for a number of terminal alkenes bearing various functional groups. In one case, the enantiomeric excess of a chiral product, i.e. a 3,5-dimethylhexa-1,4-diene derivative, was determined by chiral RP-HPLC to be 78% ee.

引用

页码：3534 / 3542

页数：9

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