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Understanding the axial chirality control of quinidine-derived ammonium cation-directed O-alkylation: a computational study

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Abstract

As a privileged chiral scaffold, cinchona alkaloid and its derivatives have reached remarkable success in catalytic asymmetric organic synthesis. In addition to the wide applications of point chirality control, Smith and co-workers recently discovered a quinidine-derived ammonium cation-catalyzed O-alkylation of tetralones, providing an effective approach for the synthesis of axially chiral biaryls. Using density functional theory (DFT) calculations, we studied the reaction mechanism and origins of enantioselectivity of this novel transformation. A stepwise strategy is adopted to ensure efficient and thorough exploration of the massive conformational space of transition state. Our computations suggested that enolate oxygen forms two hydrogen bonds with the chiral ammonium catalyst, and the non-covalent interactions between the cationic benzylic fragment and the methoxy group of enolate plays a critical role in determining the enantioselectivity.

Graphical abstract: Understanding the axial chirality control of quinidine-derived ammonium cation-directed O-alkylation: a computational study

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Publication details

The article was received on 04 Sep 2018, accepted on 27 Sep 2018 and first published on 03 Oct 2018


Article type: Paper
DOI: 10.1039/C8OB02173B
Citation: Org. Biomol. Chem., 2018, Advance Article
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    Understanding the axial chirality control of quinidine-derived ammonium cation-directed O-alkylation: a computational study

    H. Li, W. Fan and X. Hong, Org. Biomol. Chem., 2018, Advance Article , DOI: 10.1039/C8OB02173B

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