Lanthanide‐Catalyzed Reversible Alkynyl Exchange by Carbon–Carbon Single‐Bond Cleavage Assisted by a Secondary Amino Group
- 11 August 2016
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 55 (38), 11485-11489
- https://doi.org/10.1002/anie.201605822
Abstract
Lanthanide-catalyzed alkynyl exchange through C−C single-bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β-alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo- and cross-dimerization of the liberated alkyne can serve as an additional driving force to shift the metathesis equilibrium to completion. This reaction is formally complementary to conventional alkyne metathesis and allows the selective transformation of internal propargylamines into those bearing different substituents on the alkyne terminus in moderate to excellent yields under operationally simple reaction conditions.Funding Information
- National Natural Science Foundation of China
- MOST of China (2012CB821600)
- Doctoral Program of Higher Education of China
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