A Rh(II)- or Ag(I)-Catalyzed Formal C–O Bond Insertion of Cyclic Hemiaminal with Aryl Diazoacetate

Abstract

A mild and facile synthetic method via convergent assembly of two reactive intermediates generated in situ has been developed. This method provides an efficient way to construct six- and seven-membered N-heterocycles containing a biaryl linkage. This reaction features a gem-difunctionalization process of diazo compounds with cyclic hemiaminals, delivering α-hydroxyl-β-amino ester derivatives with a tertiary carbon center through a formal C–O bond-insertion transformation.

Key words

metal carbene - cyclic hemiaminals - α-hydroxyl-β-amino esters - N-heterocycles - atom economy

Publication History

Received: 10 August 2021

Accepted after revision: 30 August 2021

Accepted Manuscript online:
30 August 2021

Article published online:
14 September 2021

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• 21 General Procedure for the Ag(I)-Catalyzed Formal C–O Insertion Reaction To a solution of AgOTf (25.6 mg, 10 mol%) and hemiaminal 1 (1.0 mmol) in dichloromethane (7.5 mL) was added a solution of aryldiazoacetate 2 (1.5 mmol) in dichloromethane (5.0 mL) over 15 min via a syringe pump at room temperature under argon atmosphere. The reaction was continued for an additional 2 h under these conditions. Upon completion of the reaction (monitored by TLC), the solvent was removed, and the crude product was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 30:1 to 10:1) to give 3 in high to excellent yields as a colorless oil. 3a-1: Yield: 120 mg (52%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.42–7.34 (m, 3 H), 7.25–7.18 (m, 6 H), 7.10–7.06 (m, 1 H), 7.02–6.99 (m, 3 H), 6.10 (s, 1 H), 4.95 (d, J = 13.6 Hz, 1 H), 3.85 (d,J = 13.6 Hz, 1 H), 3.75 (s, 3 H), 3.25 (brs, 1 H), 1.53 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 174.9, 155.6, 142.5, 140.3, 138.7, 135.1, 134.0, 133.4, 129.4, 129.3, 128.8, 128.7, 128.5, 127.8, 127.2, 127.1, 127.0, 127.0, 81.1, 80.6, 69.3, 53.4, 49.2, 28.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₃₀NO₅ ⁺: 460.2118; found: 460.2121. 3a-2: Yield: 94 mg (40%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.56 (d,J= 7.5 Hz, 1 H), 7.52 (d, J = 8.0 Hz, 3 H), 7.47–7.43 (m, 2 H), 7.37–7.34 (m, 3 H), 7.26–7.20 (m, 4 H), 6.16 (s, 1 H), 4.85 (s, 1 H), 3.87 (d,J= 14.0 Hz, 1 H), 3.50 (s, 3 H), 1.19 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 173.5, 155.3, 141.9, 140.2, 138.8, 135.5, 135.2, 132.2, 129.8, 129.7, 128.8, 128.5, 128.4, 128.2, 127.8, 127.5, 127.5, 126.6, 82.4, 80.5, 68.3, 52.9, 49.3, 28.1. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₈H₃₀NO₅ ⁺: 460.2118; found: 460.2126. General Procedure for Rh(II)-Catalyzed Formal C–O Insertion Reaction To a solution of Rh₂(OAc)₄ (8.8 mg, 2 mol%) and hemiaminal 4 (1.0 mmol) in 1,2-dichloroethane (7.5 mL) was added a solution of aryldiazoacetate 2 (1.5 mmol) in dichloromethane (5.0 mL) over 20 min via a syringe pump at room temperature under argon atmosphere. The reaction was continued for an additional 2 h under these conditions. After the reaction completed (monitored by TLC), the solvent was removed, and the crude product was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 25:1 to 5:1) to give 5 in high to excellent yields as colorless oil. 5a-1: Yield: 195 mg (43%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.77–7.71 (m, 4 H), 7.42 (s, 1 H), 7.32–7.18 (m, 6 H), 6.91 (t, J = 7.4 Hz, 1 H), 6.39 (d, J = 7.6 Hz, 1 H), 6.34 (s, 1 H), 3.84 (s, 3 H), 3.19 (s, 1 H), 1.47 (s, 9 H); ¹³C NMR (100 MHz, CDCl₃): δ = 174.1, 153.0, 137.9, 135.8, 132.8, 131.9, 129.5, 128.2, 128.1, 128.0, 127.3, 127.2, 126.7, 126.6, 125.0, 123.3, 123.0, 83.2, 81.7, 61.8, 53.5, 28.2. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₇H₂₇NNaO₅ ⁺: 468.1781; found: 468.1781. 5a-2: Yield: 201 mg (46%); white solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.84 (d, J = 8.0 Hz, 1 H), 7.75 (d,J = 7.6 Hz, 1 H), 7.68 (d,J = 6.8 Hz, 2 H), 7.40 (t,J = 7.4 Hz, 1 H), 7.34–7.19 (m, 7 H), 6.96 (s, 1 H), 6.58 (s, 1 H), 3.81 (s, 3 H), 3.03 (s, 1 H), 1.26 (s, 9 H); ¹³C NMR (100 MHz, CDCl₃): δ = 173.4, 152.7, 138.1, 136.1, 133.5, 132.7, 129.2, 128.6, 128.0, 127.6, 127.5, 127.0, 126.6, 126.5, 124.5, 123.4, 122.9, 83.8, 81.4, 77.3, 53.4, 28.0. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₇H₂₇NNaO₅ ⁺: 468.1781; found: 468.1781.