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

Olivier Viudes; Alejandro Guarnieri-Ibáñez; Céline Besnard; Jérôme Lacour

doi:10.1055/a-2072-4537

Synlett, Inhaltsverzeichnis

Synlett 2023; 34(12): 1472-1476
DOI: 10.1055/a-2072-4537

cluster

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

^aDepartment of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva 4, Switzerland

,

Alejandro Guarnieri-Ibáñez

^aDepartment of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva 4, Switzerland

,

Céline Besnard

^bLaboratory of Crystallography, University of Geneva, Quai E. Ansermet 24, 1211 Geneva 4, Switzerland

,

Jérôme Lacour ∗

^aDepartment of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva 4, Switzerland

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Abstract

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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

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Referenzen

References and Notes

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6 This aspect was probed later in the manuscript with the reactivity of 1a with oxazolidine 2C′ carrying a tosyl EWG in place of the p-tolyl moiety of 2A. In the presence of this protected and thus less Lewis basic N-atom, dirhodium catalysis could occur at 40 °C only to afford 4aC′ in 93% NMR yield.
7 Triazole 1e has been rarely used for α-imino carbene generation, and this exclusively in the context of Tröger base chemistry; see ref. 5aa.

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11 CCDC 2241633 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
12 Contrary to the reactions with 2A that present excellent conversions, crude mixture analysis indicated a large proportion of unreacted starting 2B with a ca. 3:1 ratio between 3aB and 2B. See the Supporting Information.
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]⁺.

14a Musonda CC, Edlin CD, Boyle GA. WO2013072903, 2013
14b Embrey MW, Hartingh TJ, Labroli M, Raheem IT. WO2019160783, 2019

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