Direct observation of β-alkynyl eliminations from unstrained propargylic alkoxide Cu(i) complexes by C-C bond cleavage.

ABSTRACT: β-Carbon eliminations of aryl, allylic, and propargylic alkoxides of Rh(i), Pd(ii), and Cu(i) are key elementary reactions in the proposed mechanisms of homogeneously catalysed cross-coupling, group transfer, and annulation. Besides the handful of studies with isolable Rh(i)-alkoxides, β-carbon eliminations of Pd(ii)- and Cu(i)-alkoxides are less definitive. Herein, we provide a comprehensive synthetic, structural, and mechanistic study on the β-alkynyl eliminations of isolable secondary and tertiary propargylic alkoxide Cu(i) complexes, LCuOC(H)(Ph)C[triple bond, length as m-dash]CPh and LCuOC(Ar^F)₂C[triple bond, length as m-dash]CPh (L = N-heterocyclic carbene (NHC), dppf, S-BINAP), to produce monomeric (NHC)CuC[triple bond, length as m-dash]CPh, dimeric [(di

SUBMITTER: Tran BL 

PROVIDER: S-EPMC11447594 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature