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Synthesis of medium-sized benzo[b]azocines and benzo[b]azonines by photoinduced 8-/9-endo sulfonyl-cyclization

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Abstract

An efficient photochemical radical sulfonyl cyclization of designed dienes to medium-sized benzo[b]azocines and benzo[b] azonines was developed. This chemoselective method provides new highly functionalized eight- and nine-membered N-het-erocycles. Radical inhibition experiments, light on/off experiments, and apparent quantum efficiency calculations were used to clarify the radical mechanism. Density functional theory calculations enabled rationalization of the rate-determining step and observed chemoselectivity. Large-scale synthesis and derivatizations via epoxidation and convenient N-Ts deprotection showed the potential utility of this strategy. This photochemical method for synthesizing sulfonylbenzo[b]azocines and sulfonylbenzo[b] azonines with insertion of sulfur dioxide provides new sustainable routes for the synthesis of valuable medium-sized N-heterocycles.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21801007) and Qingchuang Technology Support Program of University in Shandong Province (2021KJ066). S.-F. Ni acknowledges funding from the STU Scientific Research Foundation for Talents (NTF20022).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, China

    Kai Sun & Dongyang Zhao

  2. College Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063, China

    Quanxin Li & Shaofei Ni

  3. Department of Chemistry, Northeast Normal University, Changchun, 130024, China

    Guangfan Zheng & Qian Zhang

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  1. Kai Sun
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  2. Dongyang Zhao
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Correspondence to Kai Sun, Shaofei Ni or Qian Zhang.

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Sun, K., Zhao, D., Li, Q. et al. Synthesis of medium-sized benzo[b]azocines and benzo[b]azonines by photoinduced 8-/9-endo sulfonyl-cyclization. Sci. China Chem. 66, 2309–2316 (2023). https://doi.org/10.1007/s11426-023-1622-1

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