C(sp³)O Bond‐Forming Reductive Elimination of Ethers from Bisphosphine‐Ligated Benzylpalladium(II) Aryloxide Complexes

Abstract

On the contrary: Isolated benzylpalladium aryloxide complexes undergo C(sp3)O bond‐forming reductive elimination by a stepwise ionic mechanism (see scheme) distinct from the accepted concerted pathway for reductive elimination of aromatic ethers from arylpalladium(II) species. The mechanism is proposed to result from dissociation of the aryloxide ligand followed by nucleophilic attack on the benzylic carbon atom.

Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes

“…Products derived from competing C(sp 2 )-C(sp 3 ) coupling or C(sp 2 )-heteroatom coupling were not detected in the 1 H NMR spectra of the crude reaction mixtures. Notably, C(sp 3 )-heteroatom coupling reactions of this type are rare in organometallic chemistry (20)(21)(22)(30)(31)(32)(33)(34), and most previously reported examples involve second or third row metal centers. In addition, the observation of selective C(sp 3 )-heteroatom coupling is complementary to the reactivity of other oxidation states of Ni, where C(sp 2 )-heteroatom bond-formation has significant precedent (35)(36)(37).…”

Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes

“…13,14 Kinetic and stereochemical studies implied that these reactions proceed by a stepwise pathway that involves dissociation of the diarylamido ligand, followed by nucleophilic attack of the amide onto a proposed η 3 -benzylpalladium intermediate. However, reductive elimination to form an alkyl−nitrogen bond from an isolated Pd complex has not been reported, despite significant effort.…”

Einstein Visiting Fellow: J. F. Hartwig /Nichols Medal: J. Rebek, Jr. / Otto Hahn Prize and Tetrahedron Prize: M. T. Reetz

“…Hartwig’s research involves the development of new transition‐metal‐catalyzed reactions and the study of their mechanisms. He recently published in Angewandte Chemie a Minireview on ammonia in organic synthesis1a and a Communication about CO bond‐forming reactions 1b…”