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Desymmetrizing Hydroformylation of Diallylcarbinols with the Aid of a Planar‐Chiral, Catalyst‐Directing Group
Author(s) -
Breit Bernhard,
Breuninger Daniel
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200500294
Subject(s) - stereocenter , hydroformylation , chemistry , catalysis , derivatization , group (periodic table) , substrate (aquarium) , absolute configuration , pentane , stereochemistry , rhodium , organic chemistry , enantioselective synthesis , oceanography , high performance liquid chromatography , geology
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)