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[(BINAP)Re(O)Cl-3] as an efficient catalyst for olefination of chiral alpha-substituted aliphatic aldehydes

Strand, Daniel LU and Rein, Tobias (2010) In Journal of Organometallic Chemistry 695(19-20). p.2220-2224
Abstract
A convenient one-pot preparation of [(BINAP) Re(O)Cl-3] (6) is described. This complex was demonstrated to be an efficient catalyst for the olefination of aldehydes by reaction with alpha-diazo esters, with essentially quantitative yields and up to 98:2 geometric selectivity. The potential for using enantiopure [(BINAP)Re(O)Cl-3] (6) to promote an asymmetric kinetic resolution of racemic alpha-stereogenic aldehydes was investigated, but no enantiotopic discrimination was observed. Control experiments indicate that this lack of selectivity stems from the in-situ formation of a phosphonium ylide, which accounts for product formation in a non-metal associated reaction pathway. (C) 2010 Elsevier B. V. All rights reserved.
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Rhenium, Alkenes, Homogenous catalysis, Wittig reactions
in
Journal of Organometallic Chemistry
volume
695
issue
19-20
pages
2220 - 2224
publisher
Elsevier
external identifiers
  • wos:000280847000009
  • scopus:77955710542
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2010.06.008
language
English
LU publication?
yes
id
e7c39cd9-6272-4d66-b5ab-c801beea1a07 (old id 1675437)
date added to LUP
2010-09-22 08:57:42
date last changed
2018-05-29 09:26:17
@article{e7c39cd9-6272-4d66-b5ab-c801beea1a07,
  abstract     = {A convenient one-pot preparation of [(BINAP) Re(O)Cl-3] (6) is described. This complex was demonstrated to be an efficient catalyst for the olefination of aldehydes by reaction with alpha-diazo esters, with essentially quantitative yields and up to 98:2 geometric selectivity. The potential for using enantiopure [(BINAP)Re(O)Cl-3] (6) to promote an asymmetric kinetic resolution of racemic alpha-stereogenic aldehydes was investigated, but no enantiotopic discrimination was observed. Control experiments indicate that this lack of selectivity stems from the in-situ formation of a phosphonium ylide, which accounts for product formation in a non-metal associated reaction pathway. (C) 2010 Elsevier B. V. All rights reserved.},
  author       = {Strand, Daniel and Rein, Tobias},
  issn         = {0022-328X},
  keyword      = {Rhenium,Alkenes,Homogenous catalysis,Wittig reactions},
  language     = {eng},
  number       = {19-20},
  pages        = {2220--2224},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {[(BINAP)Re(O)Cl-3] as an efficient catalyst for olefination of chiral alpha-substituted aliphatic aldehydes},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2010.06.008},
  volume       = {695},
  year         = {2010},
}