First Isolation and Characterization of the Highly Coordinated Group 14 Enolates: Effects of the Coordination Controls on the Geometry and Tautomerization of Germyl Enolates. Issue 36 (28th July 2016)

• Record Type: Journal Article
• Authors: Konishi, Akihito; Minami, Yohei; Hosoi, Takahisa; Chiba, Kouji; Yasuda, Makoto
• Is Part Of: Chemistry. Volume 22:Issue 36(2016)
• Page Start: 12688
• Page End: 12691
• Publication Date: 2016-07-28
• Subjects: germanium -- germyl enolate -- highly coordinated enolate -- reaction order -- tautomerization; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603147
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The Group 14 enolates play an important part in many organic reactions. Herein, the reduction of an α‐bromo ketone with germanium(II) salts cleanly afforded the corresponding germyl enolate as an isolatable species. This experimental reductive generation of a germyl enolate enabled us to characterize both C ‐ and O ‐bound tautomers derived from an identical precursor and to unveil the tautomeric mechanisms, including the kinetic parameters and the relative stability of these tautomers, along with confirmation from DFT calculations. Moreover, the highly coordinated germyl enolates were isolated by a stabilization process induced by adding ligands. All products were characterized by NMR spectroscopy and X‐ray crystallography. Abstract : Germynate that enolate ! Full characterization of germyl enolates was accomplished. The experimental reductive generation of a germyl enolate enabled the characterization of both C ‐ and O ‐bound tautomers derived from an identical precursor and to unveil the tautomeric mechanisms (see figure). Moreover, the highly coordinated enolates of the germyl enolates were isolated by the stabilization of additive ligands.