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. 2023 Feb 6;14(9):2330-2335.
doi: 10.1039/d2sc07103g. eCollection 2023 Mar 1.

Enantioselective construction of triaryl-substituted all-carbon quaternary stereocenters via organocatalytic arylation of oxindoles with azonaphthalenes

Pengquan Chen  1   2 , Mei-Jun Lv  2 , Jun Kee Cheng  2 , Shao-Hua Xiang  2 , Xiang-Zhong Ren  1 , Junmin Zhang  1 , Bin Tan  2
Affiliations

Enantioselective construction of triaryl-substituted all-carbon quaternary stereocenters via organocatalytic arylation of oxindoles with azonaphthalenes

Pengquan Chen et al. Chem Sci. .

Abstract

Azonaphthalenes have been verified as a class of effective arylation reagents in a variety of asymmetric transformations. Here a highly efficient approach to construct triaryl-substituted all-carbon quaternary stereocenters through chiral phosphoric acid-catalyzed enantioselective arylation of 3-aryl-2-oxindoles with azonaphthalenes is disclosed. This chemistry is scalable and displays excellent functional group tolerance, furnishing a series of 3,3-disubstituted 2-oxindole derivatives in good yields with excellent enantiocontrol. Preliminary mechanistic data suggest that the initially formed direct addition intermediate undergoes intramolecular annulation under acidic reaction conditions.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Representative catalytic asymmetric construction triaryl-substituted all-carbon quaternary centers and our design.
Scheme 2
Scheme 2. Substrate generality of the CPA catalyzed enantioselective arylation reaction. Reaction conditions: 1 (0.20 mmol), 2 (0.22 mmol), (S)-C10 (10 mol%) in toluene (4 mL) at 80 °C for 24 h under argon, unless noted otherwise. Yield of the isolated product is given. The ee values were determined by HPLC analysis using a chiral stationary phase. aReaction was carried out at 25 °C for 48 h.
Scheme 3
Scheme 3. Gram-scale synthesis and mechanistic investigations.
Scheme 4
Scheme 4. Proposed reaction mechanism and stereocontrol mode.
See this image and copyright information in PMC

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