Regiodivergent Synthesis of Oxadiazocines via Dirhodium-Catalyzed Reactivity of Oxazolidines and α-Imino Carbenes

Dedicated to Prof. Masahiro Murakami on the occasion of his 65^th birthday

Abstract

Using electron-rich or electron-poor N-substituted oxazolidines as substrates, selective formation of either ammonium or oxonium ylides is possible in the presence of α-imino carbenes. As such, treatment of 5-membered oxazolidine precursors with N-sulfonyl-1,2,3-triazoles under dirhodium catalysis (2 mol%) affords the regiodivergent synthesis of either 8-membered 1,3,6- or 1,4,6-oxadiazocines upon the initial N or O reactivity with the carbene.

Key words

carbenes - diazaoxa heterocycles - 8-membered rings - regiodivergency - Rh(II) catalysis - triazoles - ylides

Publication History

Received: 24 February 2023

Accepted after revision: 12 April 2023

Accepted Manuscript online:
12 April 2023

Article published online:
31 May 2023

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• 13 General Procedure for Ring ExpansionIn a screw-cap vial containing oxazolidine 2A (0.2 mmol, 1 equiv) and N-sulfonyl-1,2,3-triazole 1a (0.3 mmol, 1.5 equiv), Rh₂(OPiv)₄ (0.004 mmol, 0.02 equiv) in CH₂Cl₂ (0.8 mL) were added. The reaction mixture is stirred during 15 h at 60 °C. The solvent was removed under reduced pressure, and the crude residue was purified on chromatography column over SiO₂ (pentane/Et₂O, 9:1 to 8:2). R_f = 0.24 (SiO₂; pentane/Et₂O, 8:2); mp 165–167 °C. ¹H NMR (500 MHz, CDCl₃): δ = 2.15 (s, 3 H, CH₃), 2.43 (s, 3 H, CH₃), 3.38–3.50 (m, 2 H, CH₂), 3.66–3.78 (m, 2 H, CH₂), 5.14 (s, 2 H, CH₂), 6.46 (d, J = 8.5 Hz, 2 H, CH aromatic), 6.74 (s, 1 H, CH vinylic), 6.89 (d, J = 8.2 Hz, 2 H, CH aromatic), 7.14–7.25 (m, 2 H, CH aromatic), 7.26–7.32 (m, 3 H, CH aromatic), 7.81 (d, J = 8.3 Hz, 2 H, CH aromatic) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 20.5 (CH₃), 21.7 (CH₃), 52.1 (CH₂), 64.7 (CH₂) 75.8 (CH₂), 117.4 (2 CH aromatic), 117.6 (CH aromatic), 126.4 (2 CH aromatic), 127.6 (CH vinyl), 127.9 (CH aromatic), 128.5 (2 CH aromatic), 128.6 (C vinyl), 129.6 (2 CH aromatic), 130 (2 CH aromatic), 131.8 (C aromatic), 137 (C aromatic), 138.1 (C aromatic), 141.2 (C aromatic), 143.9 (C aromatic) ppm. IR (neat): ν = 3851, 3067, 2862, 1592, 1575, 1510, 1444, 1389, 1350, 1300, 1257, 1156, 1128,1097, 1013, 966, 932, 912, 887, 837, 800, 762, 694, 671, 636, 604, 567 cm^–1. HRMS (ESI): m/z calcd for C₂₅H₂₆N₂O₄S⁺: 451.1687; found: 451.1681 [M + H]⁺.
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