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Synthesis 2014; 46(21): 2897-2909
DOI: 10.1055/s-0034-1379209
DOI: 10.1055/s-0034-1379209
feature article
Homologation of Isocyanates with Lithium Carbenoids: A Straightforward Access to α-Halomethyl- and α,α-Dihalomethylamides
Further Information
Publication History
Received: 02 July 2014
Accepted after revision: 03 September 2014
Publication Date:
06 October 2014 (online)
Abstract
Treatment of widely available isocyanates with monohalolithium and dihalolithium carbenoids provides a valuable protocol for the one-pot preparation of α-halo- and α,α-dihaloacetamide derivatives. While monohalolithium carbenoids can be prepared by a smooth lithium–halogen exchange, the preparation of the corresponding dihalo compounds proved to be highly dependent on the base used to realize the deprotonation, with lithium 2,2,6,6-tetramethylpiperidine emerging as optimal. The clear advantages of the procedure are: (a) broad scope of isocyanates that can be employed; (b) preservation of the optical purity when chiral materials are used; (c) divergent access to different haloamides by simply selecting the homologating agents. We also report an application of Charette’s imidoyl triflate activation of a secondary amide to the synthesis of an α-chloro ketone and 15N NMR data for selected compounds.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000084.
- Supporting Information
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References
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