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Synlett 2015; 26(17): 2381-2384
DOI: 10.1055/s-0034-1378817
DOI: 10.1055/s-0034-1378817
cluster
Investigation of the Lithiation-Trapping of an N-Boc Bispidine-Ketal: Reactivity and Diastereoselectivity
Further Information
Publication History
Received: 27 April 2015
Accepted after revision: 08 July 2015
Publication Date:
11 August 2015 (online)
This paper is dedicated to the memory of Manfred Schlosser for his numerous pioneering contributions to synthetic organometallic chemistry
Abstract
The lithiation-trapping of an N-Boc bispidine-ketal using s-BuLi/TMEDA has been studied. Key findings include an activating effect of the 4-ketal group on the lithiation and complete diastereoselectivity with methylation and Cu-mediated allylation. In contrast, reduced diastereoselectivity was noted for direct allylation and silylation; mechanistic explanations are proposed.
Key words
organolithium reagents - lithiation - stereoselective synthesis - diastereoselectivity - bispidinesSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1378817.
- Supporting Information
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References and Notes
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Exo-face attack is precedented in the nucleophilic addition to bispidine iminium ions. See: