Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/3388304
- author
- Joosten, Antoine ; Persson, Andreas K. A. ; Millet, Renaud ; Johnson, Magnus LU and Backvall, Jan-E.
- organization
- publishing date
- 2012
- 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
- Wiley-Blackwell
- external identifiers
-
- wos:000311111900034
- scopus:84869139017
- pmid:23033176
- 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
- 2016-04-01 14:17:28
- date last changed
- 2022-06-17 06:52:22
@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}},
keywords = {{amidopalladation; cyclization; oxazolidinones; oxidation; palladium}},
language = {{eng}},
number = {{47}},
pages = {{15151--15157}},
publisher = {{Wiley-Blackwell}},
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}},
doi = {{10.1002/chem.201202359}},
volume = {{18}},
year = {{2012}},
}