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Synlett 2023; 34(12): 1472-1476
DOI: 10.1055/a-2072-4537
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Special Issue Honoring Masahiro Murakami’s Contributions to Science

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

Olivier Viudes
a   Department of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva 4, Switzerland
,
Alejandro Guarnieri-Ibáñez
a   Department of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva 4, Switzerland
,
Céline Besnard
b   Laboratory of Crystallography, University of Geneva, Quai E. Ansermet 24, 1211 Geneva 4, Switzerland
,
Jérôme Lacour  ∗
a   Department of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva 4, Switzerland
› Author AffiliationsWe thank the Université de Genève and the Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung for financial support (JL: 200020-184843 and 200020-207539).
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Dedicated to Prof. Masahiro Murakami on the occasion of his 65th 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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2072-4537.
  • Supporting Information

Primary Data

    The dataset for this article can be found at the following DOI: 10.26037/yareta:3cndx4brorddfaq4rc3oq2ggke. It will be preserved for 10 years.
  • Primary Data


Publication History

Received: 24 February 2023

Accepted after revision: 12 April 2023

Accepted Manuscript online:
12 April 2023

Article published online:
31 May 2023

© 2023. Thieme. All rights reserved

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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). Rf = 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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