Synthesis 2012; 44(22): 3534-3542
DOI: 10.1055/s-0032-1316796
paper
© Georg Thieme Verlag Stuttgart · New York

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

Marion Arndt
a   Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany   eMail: Hilt@chemie.uni-marburg.de   Fax: +49(6421)2825677
,
Mehmet Dindaroğlu
b   Department für Chemie, Universität zu Köln, Greinstr. 4, 50939 Cologne, Germany
,
Hans-Günther Schmalz
b   Department für Chemie, Universität zu Köln, Greinstr. 4, 50939 Cologne, Germany
,
Gerhard Hilt*
a   Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany   eMail: Hilt@chemie.uni-marburg.de   Fax: +49(6421)2825677
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Publikationsverlauf

Received: 17. September 2012

Accepted: 18. September 2012

Publikationsdatum:
02. Oktober 2012 (online)


Abstract

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 β-4 regioisomer, the corresponding BINOL-derived ligand gave predominantly the β-1 regioisomer. The application of (E)-2-methylpenta-1,3-diene in combination with the (nonracemic) BINOL-derived ligand generated the β-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.

 
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