English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
 
 
DownloadE-Mail
  The Silicon−Hydrogen Exchange Reaction: A Catalytic σ‑Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes

Zhou, H., Bae, H. Y., Leutzsch, M., Kennemur, J. L., Bécart, D., & List, B. (2020). The Silicon−Hydrogen Exchange Reaction: A Catalytic σ‑Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes. Journal of the American Chemical Society, 142(32), 13695-13670. doi:10.1021/jacs.0c06677.

Item is

Files

show Files
hide Files
:
jacs.0c06677.pdf (Publisher version), 2MB
Name:
jacs.0c06677.pdf
Description:
-
OA-Status:
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show

Creators

show
hide
 Creators:
Zhou, Hui1, Author
Bae, Han Yong1, Author           
Leutzsch, Markus2, Author           
Kennemur, Jennifer L.1, Author           
Bécart, Diane1, Author           
List, Benjamin1, Author           
Affiliations:
1Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445585              
2Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

Content

show
hide
Free keywords: -
 Abstract: The use of chiral enol silanes in fundamental transformations such as Mukaiyama aldol, Michael, and Mannich reactions as well as Saegusa–Ito dehydrogenations has enabled the chemical synthesis of enantiopure natural products and valuable pharmaceuticals. However, accessing these intermediates in high enantiopurity has generally required the use of either stoichiometric chiral precursors or stoichiometric chiral reagents. We now describe a catalytic approach in which strongly acidic and confined imidodiphosphorimidates (IDPi) catalyze highly enantioselective interconversions of ketones and enol silanes. These “silicon–hydrogen exchange reactions” enable access to enantiopure enol silanes via tautomerizing σ-bond metatheses, either in a deprotosilylative desymmetrization of ketones with allyl silanes as the silicon source or in a protodesilylative kinetic resolution of racemic enol silanes with a carboxylic acid as the silyl acceptor.

Details

show
hide
Language(s): eng - English
 Dates: 2020-06-212020-08-032020-08-12
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.0c06677
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (32) Sequence Number: - Start / End Page: 13695 - 13670 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870