Synlett, Table of Contents Synlett 2024; 35(03): 325-329DOI: 10.1055/a-2153-6687 cluster Organic Chemistry Under Visible Light: Photolytic and Photocatalytic Organic Transformations Visible-Light-Promoted Synthesis of Vinyloxaziridines from Conjugated Carbonyls Authors Brooke E. Austin Ryan P. Palner Elissa M. Tobias Rufai Madiu Erin L. Doran Jenna M. Doran Amari M. Howard James L. Stroud Morgan E. Rossi Dylan A. Moskovitz Dominic A. Rivera Michael D. Mullen Amy H. Zinsky Rose A. Rosario Gustavo Moura-Letts∗ Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract We report the first visible-light-promoted synthesis of vinyloxaziridines from simple conjugated nitrones. We have found that vinyl nitrones formed by the condensation reaction between conjugated carbonyls and hydroxylamines undergo visible-light-promoted energy-transfer isomerization to the respective vinyloxaziridines in very high yields and selectivities. The reaction scope expands to a large array of substitution patterns, and evidence indicates that the proposed energy-transfer pathway is the predominant mechanism for this transformation. Key words Key wordsphotoisomerization - oxaziridines - nitrones - visible light - single-electron transfer Full Text References References and Notes 1a Williamson KS, Michaelis DJ, Yoon TP. Chem. Rev. 2014; 114: 8016 1b Wang H.-H, Wang X.-D, Yin G.-F, Zeng Y.-F, Chen J, Wang Z. ACS Catal. 2022; 12: 2330 1c Sakakibara Y, Murakami K. ACS Catal. 2022; 12: 1857 1d Karmakar A, Yu P.-C, Shajan FJ, Chatare VK, Sabbers WA, Sproviero EM, Andrade RB. Org. Lett. 2022; 24: 6548 1e Behnke NE, Kielawa R, Kwon D.-H, Ess DH, Kürti L. Org. Lett. 2018; 20: 8064 1f Ghosh A, Mandal S, Chattaraj PK, Banerjee P. Org. Lett. 2016; 18: 4940 1g Motiwala HF, Gulgeze B, Aubé J. J. Org. Chem. 2012; 77: 7022 1h Williamson KS, Yoon TP. J. Am. Chem. Soc. 2010; 132: 4570 1i Williamson KS, Yoon TP. J. Am. Chem. 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The mixture was exposed to a white LED, and the reaction was monitored by TLC. The resulting mixture was purified by chromatography (silica gel). 2-Benzyl-3-[(E)-2-phenylvinyl]oxaziridine (2d): Prepared from nitrone 1d (0.1 mmol) by the general protocol and purified by automated flash chromatography [silica gel (10 g cartridge), heptanes–EtOAc (20:1 to 1:1, 14 mL/min, 12 min)] as a clear oil; yield: 23 mg (98%); TLC: Rf 0.58 (heptanes–EtOAc, 3:1). IR (thin film) 3104, 3041, 2992, 1654, 1520, 1498, 1464, 1281, 1201 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.47–7.32 (m, 10 H), 7.01 (d, J = 16.0 Hz, 1 H), 5.98 (dd, J = 16.0, 7.1 Hz, 1 H), 4.40 (d, J = 7.1 Hz, 1 H), 4.06 (d, J = 8.0 Hz, 1 H), 3.90 (d, J = 8.0 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 138.5, 135.3, 135.2, 128.9, 128.8, 128.7, 128.6, 127.9, 126.9, 124.2, 80.9, 65.5. ESI-MS: m/z (%): (pos.) 238.1 ([M + H]+, 100); (neg) 236.1 ([M – H]–, 100). HRMS (ESI): m/z [M + H]+ calcd for C16H16NO: 238.30945; found: 238.30968. Absolute difference: 0.96 ppm. Supplementary Material Supplementary Material Supporting Information (PDF)
