title: Stereodivergent hydrogermylations of α-trifluoromethylated alkynes and their applications in cross-coupling reactions.
abstract: The hydrometalation of alkynes with group 14 elements such as tin- or silyl hydrides is a classical transformation in organic synthesis. Strangely, among the group 14 elements, the use of germanium hydrides is rarely seen. Two efficient, stereodivergent, and broadly applicable routes to (Z)- and (E)-α-CF3-vinylgermanes by regio- and stereoselective hydrogermylation of α-trifluoromethylated alkynes under radical or transition-metal-catalyzed conditions are reported. Furthermore, we demonstrate that the resulting stereodefined fluorinated building blocks are remarkable cross-coupling partners, provided that the vinylgermane is appropriately tuned electronically, as demonstrated by the synthesis of trisubstituted (Z)- and (E)-α-trifluoromethylated alkenes.
authors: †Laboratoire de Chimie Moléculaire, Université de Strasbourg, CNRS UMR 7509, ECPM, 25 rue Becquerel, 67087 Strasbourg, France.
authors: Stéphane
authors: S
authors: Schweizer
authors: †Laboratoire de Chimie Moléculaire, Université de Strasbourg, CNRS UMR 7509, ECPM, 25 rue Becquerel, 67087 Strasbourg, France.
authors: Cédric
authors: C
authors: Tresse
authors: †Laboratoire de Chimie Moléculaire, Université de Strasbourg, CNRS UMR 7509, ECPM, 25 rue Becquerel, 67087 Strasbourg, France.
authors: Philippe
authors: P
authors: Bisseret
authors: ‡Institut de Science des Matériaux de Mulhouse, Université de Haute-Alsace, CNRS UMR 7361, 15 rue Jean Starcky, 68057 Mulhouse, France.
authors: Jacques
authors: J
authors: Lalevée
authors: §Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium.
authors: Gwilherm
authors: G
authors: Evano
authors: †Laboratoire de Chimie Moléculaire, Université de Strasbourg, CNRS UMR 7509, ECPM, 25 rue Becquerel, 67087 Strasbourg, France.
authors: Nicolas
authors: N
authors: Blanchard