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Photoredox-catalyzed oxo-amination of aryl cyclopropanes.
Nat Commun 2019; 10(1):4367NC

Abstract

Cyclopropanes represent a class of versatile building blocks in modern organic synthesis. While the release of ring strain offers a thermodynamic driving force, the control of selectivity for C-C bond cleavage and the subsequent regiochemistry of the functionalization remains difficult, especially for unactivated cyclopropanes. Here we report a photoredox-coupled ring-opening oxo-amination of electronically unbiased cyclopropanes, which enables the expedient construction of a host of structurally diverse β-amino ketone derivatives. Through one electron oxidation, the relatively inert aryl cyclopropanes are readily converted into reactive radical cation intermediates, which in turn participate in the ensuing ring-opening functionalizations. Based on mechanistic studies, the present oxo-amination is proposed to proceed through an SN2-like nucleophilic attack/ring-opening manifold. This protocol features wide substrate scope, mild reaction conditions, and use of dioxygen as an oxidant both for catalyst regeneration and oxygen-incorporation. Moreover, a one-pot formal aminoacylation of olefins is described through a sequential cyclopropanation/oxo-amination.

Authors+Show Affiliations

Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, 211816, Nanjing, P. R. China.Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, 211816, Nanjing, P. R. China.Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, 211816, Nanjing, P. R. China.Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, 211816, Nanjing, P. R. China.Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA, 19104, USA. pwalsh@sas.upenn.edu.Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, 211816, Nanjing, P. R. China. iamcfeng@njtech.edu.cn.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31554813

Citation

Ge, Liang, et al. "Photoredox-catalyzed Oxo-amination of Aryl Cyclopropanes." Nature Communications, vol. 10, no. 1, 2019, p. 4367.
Ge L, Wang DX, Xing R, et al. Photoredox-catalyzed oxo-amination of aryl cyclopropanes. Nat Commun. 2019;10(1):4367.
Ge, L., Wang, D. X., Xing, R., Ma, D., Walsh, P. J., & Feng, C. (2019). Photoredox-catalyzed oxo-amination of aryl cyclopropanes. Nature Communications, 10(1), p. 4367. doi:10.1038/s41467-019-12403-2.
Ge L, et al. Photoredox-catalyzed Oxo-amination of Aryl Cyclopropanes. Nat Commun. 2019 Sep 25;10(1):4367. PubMed PMID: 31554813.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Photoredox-catalyzed oxo-amination of aryl cyclopropanes. AU - Ge,Liang, AU - Wang,Ding-Xing, AU - Xing,Renyi, AU - Ma,Di, AU - Walsh,Patrick J, AU - Feng,Chao, Y1 - 2019/09/25/ PY - 2019/05/22/received PY - 2019/09/03/accepted PY - 2019/9/27/entrez PY - 2019/9/27/pubmed PY - 2019/9/27/medline SP - 4367 EP - 4367 JF - Nature communications JO - Nat Commun VL - 10 IS - 1 N2 - Cyclopropanes represent a class of versatile building blocks in modern organic synthesis. While the release of ring strain offers a thermodynamic driving force, the control of selectivity for C-C bond cleavage and the subsequent regiochemistry of the functionalization remains difficult, especially for unactivated cyclopropanes. Here we report a photoredox-coupled ring-opening oxo-amination of electronically unbiased cyclopropanes, which enables the expedient construction of a host of structurally diverse β-amino ketone derivatives. Through one electron oxidation, the relatively inert aryl cyclopropanes are readily converted into reactive radical cation intermediates, which in turn participate in the ensuing ring-opening functionalizations. Based on mechanistic studies, the present oxo-amination is proposed to proceed through an SN2-like nucleophilic attack/ring-opening manifold. This protocol features wide substrate scope, mild reaction conditions, and use of dioxygen as an oxidant both for catalyst regeneration and oxygen-incorporation. Moreover, a one-pot formal aminoacylation of olefins is described through a sequential cyclopropanation/oxo-amination. SN - 2041-1723 UR - https://www.unboundmedicine.com/medline/citation/31554813/Photoredox_catalyzed_oxo_amination_of_aryl_cyclopropanes_ L2 - http://dx.doi.org/10.1038/s41467-019-12403-2 DB - PRIME DP - Unbound Medicine ER -