Radical Germylzincation of α‑Heteroatom-Substituted Alkynes

The regio- and stereoselective addition of germanium and zinc across the C–C triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal and internal alkynes is achieved by reaction with a combination of R3GeH and Et2Zn. Diagnostic experiments support a radical-chain mechanism an...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2018-12, Vol.140 (50), p.17632-17642
Main Authors: de la Vega-Hernández, Karen, Romain, Elise, Coffinet, Anais, Bijouard, Kajetan, Gontard, Geoffrey, Chemla, Fabrice, Ferreira, Franck, Jackowski, Olivier, Perez-Luna, Alejandro
Format: Article
Language:English
Subjects:
Chemical Sciences
Organic chemistry
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Summary:The regio- and stereoselective addition of germanium and zinc across the C–C triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal and internal alkynes is achieved by reaction with a combination of R3GeH and Et2Zn. Diagnostic experiments support a radical-chain mechanism and the β-zincated vinylgermanes that show exceptional stability are characterized by NMR spectroscopy and X-ray crystallography. The unique feature of this new radical germylzincation reaction is that the C­(sp2)–Zn bond formed remains available for subsequent in situ Cu­(I)- or Pd(0)-mediated C–C or C–heteroatom bond formation with retention of the double bond geometry. These protocols offer modular access to elaborated tri- and tetrasubstituted vinylgermanes decorated with heteroatom substituents β to germanium that are useful for the preparation of stereodefined alkenes.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b09851