Palladium-N-Heterocyclic Carbene (NHC)-Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp<sup>3</sup>)—H Activation: Scope and DFT Study

Katayev, Dmitry; Larionov, Evgeny; Nakanishi, Masafumi; Besnard, Céline; Kundig, Ernst Peter

doi:10.1002/chem.201403985

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Title		Palladium-N-Heterocyclic Carbene (NHC)-Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp³)—H Activation: Scope and DFT Study
Authors		Katayev, Dmitry Larionov, Evgeny Nakanishi, Masafumi Besnard, Céline Kundig, Ernst Peter
Published in		Chemistry - A European Journal. 2014, vol. 20, no. 46, p. 15021 - 15030
Abstract		Two bulky, chiral, monodentate N-heterocyclic carbene ligands were applied to palladium-catalyzed asymmetric C—H arylation to incorporate C(sp3)—H bond activation. Racemic mixtures of the carbamate starting materials underwent regiodivergent reactions to afford different trans-2,3-substituted indolines. Although this CAr—Calkyl coupling requires high temperatures (140–160 °C), chiral induction is high. This regiodivergent reaction, when carried out with enantiopure starting materials, can lead to single structurally different enantiopure products, depending on the catalyst chirality. The C—H activation at a tertiary center was realized only in the case of a cyclopropyl group. No C—H activation takes place alpha to a tertiary center. A detailed DFT study is included and analyses of methyl versus methylene versus methine C—H activation is used to rationalize experimentally observed regio- and enantioselectivities.
Identifiers		DOI: 10.1002/chem.201403985
Full text		Article (Published version) (776 Kb) - Limited access to UNIGE
Structures		Faculté des sciences / Section de chimie et biochimie / Département de chimie organique
Citation (ISO format)		KATAYEV, Dmitry et al. Palladium-N-Heterocyclic Carbene (NHC)-Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp³)—H Activation: Scope and DFT Study. In: Chemistry - A European Journal, 2014, vol. 20, n° 46, p. 15021 - 15030. doi: 10.1002/chem.201403985 https://archive-ouverte.unige.ch/unige:41531