Organocatalytic, Chemoselective, and Stereospecific House–Meinwald Rearrangement of Trisubstituted Epoxides

Abstract

We present a novel method for the chemoselective House–Meinwald rearrangement of trisubstituted epoxides under mild conditions with the use of simple perfluorinated disulfonimides as Brønsted acid catalysts. We isolated the α-quaternary aldehyde products in yields of 27–97% using catalyst loadings as low as 0.5 mol% on a scale of 1 mmol. In addition, we show the stereospecific rearrangement using an enantioenriched substrate, which makes this method suitable for applications in total synthesis of natural products.

Key words

aldehyde synthesis - Brønsted acid - disulfonimide (DSI) - epoxide - House–Meinwald rearrangement - organocatalysis - quaternary carbon

Publication History

Received: 18 October 2023

Accepted after revision: 22 November 2023

Accepted Manuscript online:
22 November 2023

Article published online:
05 January 2024

• References and Notes

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• 31 1-(4-Benzoic Acid Methyl Ester)cyclopentanecarbaldehyde (11) Via Method B and 2 h reaction time; yield 191 mg (0.822 mmol, 82%); R_f = 0.25 (n-hexane/ethyl acetate, 20:1). ¹H NMR (400 MHz, CDCl₃): δ = 9.41 (s, 1 H), 8.03–8.00 (m, 2 H), 7.37–7.29 (m, 2 H), 3.91 (s, 3 H), 2.60–2.49 (m, 2 H), 1.95–1.86 (m, 2 H), 1.83–1.62 (m, 4 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 200.2, 166.9, 145.7, 130.1, 127.8, 64.1, 52.3, 32.7, 24.4 ppm. IR (ATR): 2952 (w), 2873 (w), 1716 (s), 1608 (w), 1435 (m), 1275 (s), 1186 (m), 1018 (m), 770 (m), 706 (m) cm^–1. HRMS (ESI): m/z calcd for C₁₄H₁₆O₃Na⁺: 255.0991; found: 255.0991 [M + Na]⁺.
• 32 1-(4-Cyanophenyl)cyclopentanecarbaldehyde (12) Via Method B and 2 h reaction time; yield 146 mg (0.733 mmol, 73%); R_f = 0.20 (n-hexane/ethyl acetate, 20:1). ¹H NMR (400 MHz, CDCl₃): δ = 9.39 (s, 1 H), 7.64 (dd, J = 8.7, 1.9 Hz, 3 H), 7.36 (dd, J = 8.7, 1.9 Hz, 3 H), 2.56–2.49 (m, 2 H), 1.93–1.84 (m, 4 H), 1.82–1.63 (m, 6 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 199.7, 145.9, 132.6, 128.6, 118.7, 111.2, 64.1, 32.7, 24.3 ppm. IR (ATR): 3364 (m), 2954 (m), 2874 (w), 2235 (m), 1607 (m), 1403 (m), 833 (s), 566 (s) cm^–1. HRMS (ESI): m/z calcd for C₁₃H₁₃NONa⁺: 222.0889; found: 222.0890 [M + Na]⁺.
• 33 1-(4-Nitrophenyl)cyclopentanecarbaldehyde (13) Via Method B and 2 h reaction time; yield 160 mg (0.730 mmol, 75%); R_f = 0.22 (n-hexane/ethyl acetate, 10:1). ¹H NMR (400 MHz, CDCl₃): δ = 9.43 (s, 1 H), 8.21 (dd, J = 8.9, 2.1 Hz, 2 H), 7.43 (dd, J = 8.9, 2.1 Hz, 2 H), 2.61–2.53 (m, 2 H), 1.98–1.89 (m, 2 H), 1.85–1.65 (m, 5 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 199.6, 148.0, 147.2, 128.7, 124.0, 64.1, 33.0, 24.4 ppm. IR (ATR): 3108 (w), 3080 (w), 2944 (m), 1720 (s), 1595 (m), 1513 (s), 1347 (s) 1317 (m), 1108 (m), 851 (m), 748 (m), 696 (s) cm^–1. HRMS (ESI): m/z calcd for C₁₂H₁₃NO₃Na⁺: 242.0787; found: 242.0790 [M + Na]⁺.
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• 36 Ethyl-(3R)-(3-phenyl-3-formyl-1-pyrrolidinecarboxylate) ((R)-14) Via Method B on a 1.5 mmol scale with 0.5 mol% catalyst and 15 min reaction time; yield 360 mg (1.46 mmol, 97%); R_f = 0.22 (n-hexane/ethyl acetate, 5:1). ¹H NMR (400 MHz, CDCl₃): δ = 9.45 (s, 1 H), 7.44–7.37 (m, 2 H), 7.36–7.30 (m, 1 H), 7.24–7.17 (m, 2 H), 4.47–4.35 (m, 1 H), 4.22–4.09 (m, 2 H), 3.70–3.47 (m, 2 H), 3.35 (td, J = 10.7, 6.9 Hz, 1 H), 2.81 (br s, 1 H), 2.21 (q, J = 10.7 Hz, 1 H), 1.63 (br s, 1 H), 1.31–1.24 (m, 3 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 198.0, 155.1, 136.3, 129.4, 128.3, 127.4, 106.3, 61.4, 50.2, 44.8, 30.8, 14.9 ppm. IR (ATR): 2989 (w), 2878 (w), 2809 (w), 1718 (m), 1694 (s), 1419 (s), 1380 (m), 1354 (m), 1341 (m), 1103 (m), 1024 (m), 888 (w), 769 (m), 759 (m), 699 (m) cm⁻¹. HRMS (ESI): m/z calcd for C₁₄H₁₇NO₃Na⁺: 270.1100; found: 270.1102 [M + Na]⁺. HPLC: Chiralpak IC (n-hexane/2-propanol, 70:30 v/v, 1 mL/min, 30 min run time), fraction 1: t _R = 11.59 min, fraction 2: t _R = 14.65 min.