Expedient Access to Structural Complexity via Radical β-Fragmentation of N–O Bonds

Xingheng Yang; Chi Zhang; Cheng-Qiang Wang; Chao Feng

doi:10.1055/a-2504-3639

Synlett, Table of Contents

Synlett 2025; 36(09): 1135-1141
DOI: 10.1055/a-2504-3639

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Expedient Access to Structural Complexity via Radical β-Fragmentation of N–O Bonds

Xingheng Yang

^aTechnical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. of China

,

Chi Zhang

^aTechnical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. of China

,

Cheng-Qiang Wang∗

^aTechnical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. of China

,

Chao Feng∗

^aTechnical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. of China

^bState Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. of China

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Abstract

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Abstract

Structures containing N–O bonds are well-established precursors of nitrogen- and/or oxygen-centered radicals under visible-light conditions in modern organic synthesis. Whereas both heterolytic and homolytic scissions of N–O bonds have been extensively documented, intrinsic limitations related to substrate structure somewhat restrict their broader application. This paper highlights a novel strategy that synergistically combines a radical-generation process that is independent of the substrate’s redox potential with a radical-induced β-fragmentation of the N–O bond. Subsequent manipulation of the generated nitrogen- or oxygen-centered radicals leads to the successful development of group-transfer carboamination of alkenes, ring-opening functionalization of heterocycles, and efficient trifunctionalization of nonactivated alkenes.

1 Introduction

2 Carboamination of Nonactivated Alkenes

3 Radical-Addition-Induced Ring-Opening Functionalization of 4-Isoxazolines

4 Multisite Functionalization of Alkenes by Merging Cycloaddition and Ring-Opening Functionalization

5 Conclusion

Key words

β-fragmentation - N–O bond scission - radical reactions - halogen-atom transfer - remote functionalization

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References

References

1a Zard SZ. Chem. Soc. Rev. 2008; 37: 1603
1b Xiong T, Zhang Q. Chem. Soc. Rev. 2016; 45: 3069
1c Guo J.-J, Hu A, Zuo Z. Tetrahedron Lett. 2018; 59: 2103
1d Jia K, Chen Y. Chem. Commun. 2018; 54: 6105
1e Chang L, An Q, Duan L, Feng K, Zuo Z. Chem. Rev. 2022; 122: 2429
1f Zhu X, Fu H. Chem. Commun. 2021; 57: 9656
1g Xiao F, Guo Y, Zeng Y.-F. Adv. Synth. Catal. 2021; 363: 120

2a Nakamura I, Terada M. Heterocycles 2014; 89: 845
2b Li J, Hu Y, Zhang D, Liu Q, Dong Y, Liu H. Adv. Synth. Catal. 2017; 359: 710
2c Lei L, Li C, Mo D. Youji Huaxue 2019; 39: 2989
2d Rykaczewski KA, Wearing ER, Blackmun DE, Schindler CS. Nat. Synth. 2022; 1: 24
2e Jiang H.-M, Zhao Y.-L, Sun Q, Ouyang X.-H, Li J.-H. Molecules 2023; 28: 1775

3a Romero NA, Nicewicz DA. Chem. Rev. 2016; 116: 10075
3b Marzo L, Pagire SK, Reiser O, König B. Angew. Chem. Int. Ed. 2018; 57: 10034
3c Skubi KL, Blum TR, Yoon TP. Chem. Rev. 2016; 116: 10035
3d Shaw MH, Twilton J, MacMillan DW. C. J. Org. Chem. 2016; 81: 6898
3e Strieth-Kalthoff F, James MJ, Teders M, Pitzer L, Glorius F. Chem. Soc. Rev. 2018; 47: 7190

4a Kärkäs MD. ACS Catal. 2017; 7: 4999
4b Chen J.-R, Hu X.-Q, Lu L.-Q, Xiao W.-J. Chem. Soc. Rev. 2016; 45: 2044
4c Kwon K, Simons RT, Nandakumar M, Roizen JL. Chem. Rev. 2022; 122: 2353

5 Davies J, Morcillo SP, Douglas JJ, Leonori D. Chem. Eur. J. 2018; 24: 12154
6 Lee DS, Soni VK, Cho EJ. Acc. Chem. Res. 2022; 55: 2526

7a Xu Y, Gao H.-X, Pan C, Shi Y, Zhang C, Huang G, Feng C. Angew. Chem. Int. Ed. 2023; 62: e202310671
7b Ge L, Zhang C, Pan C, Wang D.-X, Liu D.-Y, Li Z.-Q, Shem P, Tian L, Feng C. Nat. Commun. 2022; 13: 5938
7c Ge L, Wang D.-X, Xing R, Ma D, Walsh PJ, Feng C. Nat. Commun. 2019; 10: 4367
7d Tang H.-J, Zhang X, Zhang Y.-F, Feng C. Angew. Chem. Int. Ed. 2020; 59: 5242
7e Liu H, Ge L, Wang D.-X, Chen N, Feng C. Angew. Chem. Int. Ed. 2019; 58: 3918
7f Cai S.-H, Xie J.-H, Song S, Ye L, Feng C, Loh T.-P. ACS Catal. 2016; 6: 5571
7g Li Z.-Q, Zhang C, Feng C. Synlett 2023; 34: 393
7h Chen K, Li Z.-Q, Zhu C, Feng C. Trends Chem. 2023; 5: 160

8 Jiang H, Studer A. CCS Chem. 2019; 1: 38

9a Juliá F, Constantin T, Leonori D. Chem. Rev. 2022; 122: 2292
9b Jiang Y, Yin Y, Jiang Z. Chin. J. Org. Chem. 2024; 44: 1733

10 Zhang Y, Liu H, Tang L, Tang H.-J, Wang L, Zhu C, Feng C. J. Am. Chem. Soc. 2018; 140: 10695
11 Li X, Shui Y, Shen P, Wang Y.-P, Zhang C, Feng C. Chem 2022; 8: 2245
12 Liu H, Wang Y.-P, Wang H, Ren K, Liu L, Dang L, Wang C.-Q, Feng C. Angew. Chem. Int. Ed. 2024; 63: e202407928
13 Le C, Chen TQ, Liang T, Zhang P, MacMillan DW. C. Science 2018; 360: 1010