Diastereoselective Cross-Dehydrogenative Coupling Reactions of Amides with Diarylmethanes Using DDQ through Oxidative C–H Benzylic Activation

Abstract

This study reports the chiral-auxiliary-controlled diastereoselective dehydrogenative coupling of diarylmethanes with amides by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as the oxidant. The scope of the proposed reaction is very broad, with a wide variety of substrates and nucleophiles being applicable. The chiral induction can be attributed to the coordination of the oxygen atom on the chiral auxiliary with the carbocation intermediates.

Key words

amidation - chiral auxiliaries - C–H bond activation - dehydrogenation - diastereoselectivity

Publication History

Received: 04 August 2023

Accepted after revision: 27 September 2023

Accepted Manuscript online:
27 September 2023

Article published online:
02 November 2023

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• 10 N-[(R)-{2-[(1S)-2-methoxy-1-phenylethoxy]phenyl}(phenyl)methyl]benzamide (2a);^8d Typical Procedure (Table [2], Entry 1) Benzamide (3) (27.8 mg, 0.23 mmol) and DDQ (41.6 mg, 0.18 mmol) were added successively to a mixture of diarylmethane 1a (48.4 mg, 0.15 mmol) and 3 Å MS (100 mg) in DCE (0.5 mL) at r.t. DCE (1.0 mL) was then added to the mixture by flowing it down the wall of the flask. The resulting mixture was refluxed in an oil bath (100 °C) for 24 h, and then the reaction was quenched with sat. aq NaHCO₃ at 0 °C. The resulting mixture was diluted with CH₂Cl₂, and the organic layer was separated. The aqueous layer was extracted with EtOAc, and the organic layers were combined, dried (Na₂SO₄), filtered, and concentrated to give a crude product that was purified by preparative TLC (silica gel, hexane–EtOAc, 4:1) to give a pale-yellow oil; yield: 61.7 mg (92%, dr = 91:9). The major diastereomer was separated from the minor diastereomer by three cycles of preparative TLC (silica gel, hexane–EtOAc, 4:1). ¹H NMR (500 MHz, CDCl₃): δ = 7.89–7.82 (m, 3 H), 7.51–7.45 (m, 1 H), 7.42–7.37 (m, 3 H), 7.35–7.30 (m, 4 H), 7.28–7.24 (m, 4 H), 7.20–7.16 (m, 2 H), 7.14–7.09 (m, 1 H), 6.93 (dt, J = 1.0, 7.5 Hz, 1 H), 6.72–6.66 (m, 2 H), 5.23 (t, J = 5.0, 4.5 Hz, 1 H), 3.55 (dd, J = 10.0, 5.0 Hz, 1 H), 3.43 (dd, J = 10.0, 4.5 Hz, 1 H), 3.18 (s, 3 H). ¹³C{¹H} NMR (126 MHz, CDCl₃): δ = 166.2, 155.3, 142.0, 138.2, 134.3, 131.4, 129.8, 129.3, 128.8, 128.6, 128.4, 128.2, 128.1, 127.0, 126.8, 126.7, 126.4, 121.0, 113.5, 78.8, 76.1, 59.1, 55.1. 1 mmol-Scale Synthesis of 2a Prepared as above from diarylmethane 1a (319.4 mg, 1.00 mmol), benzamide (3; 182.3 mg, 1.50 mmol), DDQ (273.3 mg, 1.20 mmol), and 3 Å MS (650 mg) in DCE (4.0 mL + 6 mL); yield: 375.5 mg (86%, dr = 91:9). The major diastereomer was separated from the minor diastereomer by preparative TLC as above to give a pale yellowish viscous oil; yield: 313.2 mg (71%).
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