Desymmetrizing Hydroformylation of Diallylcarbinols with the Aid of a Planar-Chiral, Catalyst-Directing Group

✍ Scribed by Bernhard Breit; Daniel Breuninger

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 244 KB
• Volume: 2005
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/ejoc.200500294

✦ Synopsis

Abstract

The desymmetrizing hydroformylation of diallylcarbinols has been achieved by employing a planar‐chiral, substrate‐bound catalyst‐directing group — the ortho‐(diphenylphosphanyl)ferrocenylcarbonyl group (o‐DPPF). The method allows the simultaneous construction of two stereogenic centers in a 1,3‐relative position with high levels of stereocontrol. The diastereoselectivity was investigated as a function of substrate structure. Determination of the relative and absolute configuration of the product aldehydes (chemical derivatization and X‐ray crystallographic studies), as well as the conditions for removal and recovery of the catalyst‐directing o‐DPPF group, are described. Furthermore, a model is suggested that rationalizes the experimentally observed stereochemical result based on the minimization of syn‐pentane interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)