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Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]+

journal contribution
posted on 2023-05-18, 06:01 authored by Woolley, M, Alireza AriafardAlireza Ariafard, Khairallah, GN, Kwan, KH-Y, Donnelly, PS, White, JM, Allan CantyAllan Canty, Brian YatesBrian Yates, O'Hair, RAJ
Gas-phase carbon–carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O2CCH3)]+ (where M = Ni, Pd or Pt) formed via electrospray ionization of metal acetate complexes [(phen)M(O2CCH3)2], were examined using an ion trap mass spectrometer and density functional theory (DFT) calculations. In step 1 of the catalytic cycle, collision induced dissociation (CID) of [(phen)M(O2CCH3)]+ yields the organometallic complex, [(phen)M(CH3)]+, via decarboxylation. [(phen)M(CH3)]+ reacts with allyl acetate via three competing reactions, with reactivity orders (% reaction efficiencies) established via kinetic modeling. In step 2a, allylic alkylation occurs to give 1-butene and reform metal acetate, [(phen)M(O2CCH3)]+, with Ni (36%) > Pd (28%) > Pt (2%). Adduct formation, [(phen)M(C6H11O2)]+, occurs with Pt (24%) > Pd (21%) > Ni(11%). The major losses upon CID on the adduct, [(phen)M(C6H11O2)]+, are 1-butene for M = Ni and Pd and methane for Pt. Loss of methane only occurs for Pt (10%) to give [(phen)Pt(C5H7O2)]+. The sequences of steps 1 and 2a close a catalytic cycle for decarboxylative carbon–carbon bond coupling. DFT calculations suggest that carbon–carbon bond formation occurs via alkene insertion as the initial step for all three metals, without involving higher oxidation states for the metal centers.

History

Publication title

The Journal of Organic Chemistry

Volume

79

Issue

24

Pagination

12056-12069

ISSN

0022-3263

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

Copyright 2014 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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