A Chiral N-Tetrafluoroiodobenzyl-N-sulfonyl Aminomethylpyrrolidine Catalyst for the Enantioselective Michael/Hemiaminal Formation Cascade Reaction of α,β-Unsaturated Iminoindoles with ­Aldehydes

Abstract

A chiral N-2,3,4,5-tetrafluoro-6-iodobenzyl-N-sulfonyl ­aminomethylpyrrolidine tetrafluoroacetic acid salt was designed as an ­iodinated enamine organocatalyst for the enantioselective ­Michael/hemiaminal formation cascade reaction of α,β-unsaturated ­iminoindoles with aldehydes. The use of this iodinated enamine ­catalyst furnished anti-α-carbolinol derivatives in high yields and high stereoselectivities.

Key words

cascade reaction - catalytic asymmetric reaction - α-­carbolinol - hemiaminal formation - Michael reaction - iodo-pyrrolidine catalyst

Publication History

Received: 11 June 2022

Accepted after revision: 07 July 2022

Accepted Manuscript online:
07 July 2022

Article published online:
04 August 2022

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• 12 (2R,3R,4S)-3-Methyl-4-phenyl-1-tosyl-2,3,4,9-tetrahydro-1H-pyrido[2,3-b]indol-2-ol (4a); Typical ProcedureTo a solution of catalyst 1g (18.3 mg, 0.025 mmol) in t-BuOMe (1 mL) were added N-[3-(phenylmethylene)-3H-indole-2-yl]tosylamide (2a) (93.6 mg, 0.25 mmol) and propionaldehyde (3a) (179.3 μL, 2.5 mmol) at room temperature, and the mixture was stirred at room temperature for 48 h. Saturated aqueous NaHCO₃ solution (5 mL) was added to the mixture and the product was extracted with AcOEt (3 × 15 mL). The organic phase was washed with brine, dried over Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: hexane/Et₂O = 3:1) to give the desired product 4a (103.9 mg, 96% yield, dr = 87:13, 96% ee).Yellow solid; mp 115.0–115.5 °C. ¹H NMR (400 MHz, CDCl₃): δ = 9.01 (s, 1 H), 7.58 (d, J = 8.4 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.26 (d, J = 8.4 Hz, 2 H), 7.21–7.10 (m, 3 H), 7.09–7.01 (m, 1 H), 6.89–6.70 (m, 3 H), 6.48 (d, J = 8.0 Hz, 1 H), 5.63–5.52 (m, 1 H), 3.70 (d, J = 11.2 Hz, 1 H), 3.17 (br s, 1 H), 2.39 (s, 3 H), 1.21–1.09 (m, 1 H), 0.88 (d, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 144.8, 142.5, 134.4, 133.7, 130.1 (2 C), 128.6 (3 C), 128.2 (2 C), 126.8 (2 C), 126.6, 125.6, 121.4, 119.6, 119.1, 110.7, 102.9, 83.9, 41.2, 40.2, 21.6, 14.8. IR (neat): 3418, 1597, 1462, 1454, 1363, 1349, 1158, 984 cm^–1. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₅H₂₅N₂O₃S: 433.1580; found: 433.1577. HPLC: Daicel Chiralpak AS-H, hexane/i-PrOH = 75:25, flow rate = 0.6 mL/min, 210 nm, t _R = 26.6 min (minor, S,S,R), 38.5 min (major, R,R,S).