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Acid-induced atypical spontaneous conversion of 5-amino-2,6-dioxooctahydro-1H-pyrrolo[2,1-d][1,5]oxazocine into 4-(hydroxymethyl)-2,5-dioxooctahydro-1H-pyrrolo[1,2-d][1,4]diazepine

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Abstract

(5S,8S,10aR)-tert-butyl 5-(tert-butoxycarbonylamino)-2,6-dioxooctahydro-1H-pyrrolo[2,1-d][1,5]oxazocine-8-carboxylate 5, containing an original proline-like moiety, was prepared through Yamaguchi lactonization. However, it was observed that this 8 + 5 bicyclic lactone was spontaneously rearranged to the corresponding 7 + 5 bicyclic lactam under acid conditions, used to remove the Boc/tBu protecting groups. Both core structures were confirmed by one-dimensional and two-dimensional NMR, as well as HRMS. The new proline-like moieties are unknown up to now, and the 7 + 5 bicyclic lactam, much more stable than its precursor, may represent a valuable template to develop constrained non-peptide mimetics.

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Acknowledgments

This work was supported by the Grant 4863 from Association pour la Recherche contre le Cancer (ARC). Z.S. was supported by Guangzhou Elites Project of Guangzhou Municipal Government.

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Authors and Affiliations

  1. Institute of Natural Medicine and Green Chemistry, Guangdong University of Technology, Guangzhou, 510006, People’s Republic of China

    Zhaojun Sheng, Chang-Zhi Dong, Zhiyun Du & Kun Zhang

  2. ITODYS, UMR 7086 CNRS, Université Paris Diderot, Sorbonne Paris Cité, 15 rue J-A de Baïf, 75205, Paris Cedex 13, France

    Zhaojun Sheng, Chang-Zhi Dong, Yiming Shi & Frédérique Pallois

  3. Department of Pharmacy, Basic Medical College, Shanghai Jiaotong University, Shanghai, 200025, People’s Republic of China

    Yiming Shi & Yang Lu

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  1. Zhaojun Sheng
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  2. Chang-Zhi Dong
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Correspondence to Chang-Zhi Dong or Kun Zhang.

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Sheng, Z., Dong, CZ., Du, Z. et al. Acid-induced atypical spontaneous conversion of 5-amino-2,6-dioxooctahydro-1H-pyrrolo[2,1-d][1,5]oxazocine into 4-(hydroxymethyl)-2,5-dioxooctahydro-1H-pyrrolo[1,2-d][1,4]diazepine. Res Chem Intermed 41, 7179–7187 (2015). https://doi.org/10.1007/s11164-014-1805-4

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