Unraveling organocuprate complexity: Fundamental insights into intrinsic group transfer selectivity in alkylation reactions

Nicole J. Rijs, Naohiko Yoshikai, Eiichi Nakamura, Richard A.J. O'Hair

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

The near thermal conditions of an ion-trap mass spectrometer were used to examine the intrinsic gas-phase reactivity and selectivity of nucleophilic substitution reactions. The well-defined organocuprate anions [CH 3CuR]- (R = CH3CH2, CH 3CH2CH2, (CH3)2CH, PhCH2CH2, PhCH2, Ph, C3H 5, and H) were reacted with CH3I. The rates (reaction efficiencies,) and selectivities (the product ion branching ratios) were compared with those of [CH3CuCH3]- reacting with CH3I. Alkyl R groups yielded similar efficiencies, with selectivity for C-C bond formation at the coordinated R group. Inclusion of unsaturated R groups curbed the overall reactivity (= 1 to 2 orders of magnitude lower). With the exception of R = PhCH2CH2, these switched their selectivity to C-C bond formation at the CH3 group. Replacing an organyl ligand with R = H significantly enhanced the reactivity (8-fold), resulting in the selective formation of methane. Unique decomposition and side-reactions observed include: (1) spontaneous β-hydride elimination from [RCuI]- byproducts; and (2) homocoupling of the pre-existing organocuprate ligands in [CH3CuC3H5] -, as shown by deuterium labeling. DFT (B3LYP-D/Def2-QZVP//B3LYP/SDD: 6-31+G(d)) predicts that the alkylation mechanism for all species is via oxidative addition/reductive elimination (OA/RE). OA is the rate-limiting step, while RE determines selectivity: the effects of R on each were examined.

Original languageEnglish
Pages (from-to)1320-1334
Number of pages15
JournalJournal of Organic Chemistry
Volume79
Issue number3
DOIs
Publication statusPublished - 2014 Feb 7
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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