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Organocatalytic Vinyl and Friedel−Crafts Alkylations with Trifluoroborate Salts

Lee, Sandra and MacMillan, David W. C. (2007) Organocatalytic Vinyl and Friedel−Crafts Alkylations with Trifluoroborate Salts. Journal of the American Chemical Society, 129 (50). pp. 15438-15439. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170510-082600874

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Abstract

Herein we report the first use of vinyl and heteroaryl trifluoroborate salts as viable substrates for amine-catalyzed conjugate additions. The application of LUMO-lowering iminium catalysis has enabled the highly regio- and enantioselective 1,4-addition of rationally designed trifluoroborate salt nucleophiles to α,β-unsaturated aldehydes. Imidazolidinone 2•HCl was found to catalyze the addition of various BF_3K-derived heteroaryl and vinyl species to a range of enals with excellent levels of enantioselectivity. Importantly, the use of these salts can enable nontraditional regiocontrol as part of a Friedel−Crafts pathway. Boronic acids can also be employed as viable π-nucleophiles for these asymmetric conjugate additions provided that in situ activation to the corresponding boronate species is accomplished. While BF_3K salts are routinely employed in transition metal catalysis, to our knowledge, this is the first use of this activation group for organic catalysis or Friedel−Crafts alkylations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0767480DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0767480PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja0767480PublisherSupporting Information
Additional Information:© 2007 American Chemical Society. Received September 6, 2007. Publication Date (Web): November 22, 2007. Financial support was provided by the NIHGMS (R01 GM078201-01-01) and kind gifts from Merck. S.L. is grateful for a NPSC fellowship with Amgen.
Funders:
Funding AgencyGrant Number
NIHR01 GM078201-01-01
MerckUNSPECIFIED
AmgenUNSPECIFIED
Issue or Number:50
Record Number:CaltechAUTHORS:20170510-082600874
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170510-082600874
Official Citation:Organocatalytic Vinyl and Friedel−Crafts Alkylations with Trifluoroborate Salts Sandra Lee and David W. C. MacMillan Journal of the American Chemical Society 2007 129 (50), 15438-15439 DOI: 10.1021/ja0767480
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77329
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 May 2017 20:49
Last Modified:03 Oct 2019 17:56

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