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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Veröffentlicht in:	Journal of the American Chemical Society 2018-12, Vol.140 (50), p.17632-17642
Hauptverfasser:	de la Vega-Hernández, Karen, Romain, Elise, Coffinet, Anais, Bijouard, Kajetan, Gontard, Geoffrey, Chemla, Fabrice, Ferreira, Franck, Jackowski, Olivier, Perez-Luna, Alejandro
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Schlagworte:	Chemical Sciences Organic chemistry
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container_title	Journal of the American Chemical Society
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creator	de la Vega-Hernández, Karen Romain, Elise Coffinet, Anais Bijouard, Kajetan Gontard, Geoffrey Chemla, Fabrice Ferreira, Franck Jackowski, Olivier Perez-Luna, Alejandro
description	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.
doi_str_mv	10.1021/jacs.8b09851
format	Article
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title	Radical Germylzincation of α‑Heteroatom-Substituted Alkynes
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