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 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 All articles of this category 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
