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Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects

Joosten, Antoine; Persson, Andreas K. A.; Millet, Renaud; Johnson, Magnus LU and Backvall, Jan-E. (2012) In Chemistry: A European Journal 18(47). p.15151-15157
Abstract
A highly selective oxidative palladium(II)-catalyzed (Wacker-type) cyclization of readily available allylic tosylcarbamates is reported. This operationally simple catalytic reaction furnishes tosyl-protected vinyl-oxazolidinones, common precursors to syn-1,2-amino alcohols, in high yield and excellent diasteroselectivity (>20:1). It is demonstrated that both stoichiometric amounts of benzoquinone (BQ) as well as aerobic reoxidation (molecular oxygen) is suitable for this transformation. The title reaction is shown to proceed through overall trans-amidopalladation of the olefin followed by beta-hydride elimination. This process is scalable and the products are suitable for a range of subsequent transformations such as: kinetic resolution... (More)
A highly selective oxidative palladium(II)-catalyzed (Wacker-type) cyclization of readily available allylic tosylcarbamates is reported. This operationally simple catalytic reaction furnishes tosyl-protected vinyl-oxazolidinones, common precursors to syn-1,2-amino alcohols, in high yield and excellent diasteroselectivity (>20:1). It is demonstrated that both stoichiometric amounts of benzoquinone (BQ) as well as aerobic reoxidation (molecular oxygen) is suitable for this transformation. The title reaction is shown to proceed through overall trans-amidopalladation of the olefin followed by beta-hydride elimination. This process is scalable and the products are suitable for a range of subsequent transformations such as: kinetic resolution (KR) and oxidative Heck-, Wacker-, and metathesis reactions. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
amidopalladation, cyclization, oxazolidinones, oxidation, palladium
in
Chemistry: A European Journal
volume
18
issue
47
pages
15151 - 15157
publisher
John Wiley & Sons
external identifiers
  • wos:000311111900034
  • scopus:84869139017
ISSN
1521-3765
DOI
10.1002/chem.201202359
language
English
LU publication?
yes
id
45b3c992-07e9-4d19-9b03-ecb4fc42c1c5 (old id 3388304)
date added to LUP
2013-01-30 14:13:32
date last changed
2017-10-01 04:20:30
@article{45b3c992-07e9-4d19-9b03-ecb4fc42c1c5,
  abstract     = {A highly selective oxidative palladium(II)-catalyzed (Wacker-type) cyclization of readily available allylic tosylcarbamates is reported. This operationally simple catalytic reaction furnishes tosyl-protected vinyl-oxazolidinones, common precursors to syn-1,2-amino alcohols, in high yield and excellent diasteroselectivity (>20:1). It is demonstrated that both stoichiometric amounts of benzoquinone (BQ) as well as aerobic reoxidation (molecular oxygen) is suitable for this transformation. The title reaction is shown to proceed through overall trans-amidopalladation of the olefin followed by beta-hydride elimination. This process is scalable and the products are suitable for a range of subsequent transformations such as: kinetic resolution (KR) and oxidative Heck-, Wacker-, and metathesis reactions.},
  author       = {Joosten, Antoine and Persson, Andreas K. A. and Millet, Renaud and Johnson, Magnus and Backvall, Jan-E.},
  issn         = {1521-3765},
  keyword      = {amidopalladation,cyclization,oxazolidinones,oxidation,palladium},
  language     = {eng},
  number       = {47},
  pages        = {15151--15157},
  publisher    = {John Wiley & Sons},
  series       = {Chemistry: A European Journal},
  title        = {Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects},
  url          = {http://dx.doi.org/10.1002/chem.201202359},
  volume       = {18},
  year         = {2012},
}