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Room temperature catalytic carbon-hydrogen bond alumination of unactivated arenes: mechanism and selectivity.

ABSTRACT: We report the first catalytic methods for the transformation of C-H bonds of unactivated arenes into C-Al bonds. The catalytic reactions occur at 25 °C (benzene, toluene and xylenes) with palladium loadings as low as 0.1 mol%. Remarkably, the C-H activation of toluene and xylenes proceeds with ortho- and meta-selectivity. This selectivity is highly unusual and complementary to both Friedel-Crafts and the majority of C-H borylation methods. Through a detailed mechanistic analysis (Eyring analysis, KIE, DFT, QTAIM) we show that unusual Pd-Al intermetallic complexes are on the catalytic cycle and that the selectivity is determined by weak attractive dispersion forces in the transition state for C-H bond breaking.

SUBMITTER: Hooper TN

PROVIDER: S-EPMC6011207 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Room temperature catalytic carbon-hydrogen bond alumination of unactivated arenes: mechanism and selectivity.

Hooper Thomas N TN Garçon Martí M White Andrew J P AJP Crimmin Mark R MR

Chemical science 20180529 24

We report the first catalytic methods for the transformation of C-H bonds of unactivated arenes into C-Al bonds. The catalytic reactions occur at 25 °C (benzene, toluene and xylenes) with palladium loadings as low as 0.1 mol%. Remarkably, the C-H activation of toluene and xylenes proceeds with <i>ortho</i>- and <i>meta</i>-selectivity. This selectivity is highly unusual and complementary to both Friedel-Crafts and the majority of C-H borylation methods. Through a detailed mechanistic analysis (E ...[more]

PMID: 30155233

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Project description:Non-catalysed and catalysed reactions of aluminium reagents with furans, dihydrofurans and dihydropyrans were investigated and lead to ring-expanded products due to the insertion of the aluminium reagent into a C-O bond of the heterocycle. Specifically, the reaction of [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl, 1) with furans proceeded between 25 and 80 °C leading to dearomatised products due to the net transformation of a sp2 C-O bond into a sp2 C-Al bond. The kinetics of the reaction of 1 with furan were found to be 1st order with respect to 1 with activation parameters ΔH ‡ = +19.7 (±2.7) kcal mol-1, ΔS ‡ = -18.8 (±7.8) cal K-1 mol-1 and ΔG ‡ 298 K = +25.3 (±0.5) kcal mol-1 and a KIE of 1.0 ± 0.1. DFT calculations support a stepwise mechanism involving an initial (4 + 1) cycloaddition of 1 with furan to form a bicyclic intermediate that rearranges by an α-migration. The selectivity of ring-expansion is influenced by factors that weaken the sp2 C-O bond through population of the σ*-orbital. Inclusion of [Pd(PCy3)2] as a catalyst in these reactions results in expansion of the substrate scope to include 2,3-dihydrofurans and 3,4-dihydropyrans and improves selectivity. Under catalysed conditions, the C-O bond that breaks is that adjacent to the sp2C-H bond. The aluminium(iii) dihydride reagent [{(MesNCMe)2CH}AlH2] (Mes = 2,4,6-trimethylphenyl, 2) can also be used under catalytic conditions to effect a dehydrogenative ring-expansion of furans. Further mechanistic analysis shows that C-O bond functionalisation occurs via an initial C-H bond alumination. Kinetic products can be isolated that are derived from installation of the aluminium reagent at the 2-position of the heterocycle. C-H alumination occurs with a KIE of 4.8 ± 0.3 consistent with a turnover limiting step involving oxidative addition of the C-H bond to the palladium catalyst. Isomerisation of the kinetic C-H aluminated product to the thermodynamic C-O ring expansion product is an intramolecular process that is again catalysed by [Pd(PCy3)2]. DFT calculations suggest that the key C-O bond breaking step involves attack of an aluminium based metalloligand on the 2-palladated heterocycle. The new methodology has been applied to important platform chemicals from biomass.

Dataset Information

Room temperature catalytic carbon-hydrogen bond alumination of unactivated arenes: mechanism and selectivity.

Publications

Room temperature catalytic carbon-hydrogen bond alumination of unactivated arenes: mechanism and selectivity.

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