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Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines.
J Am Chem Soc. 2020 02 19; 142(7):3636-3644.JA

Abstract

In the past decades, significant advances have been made on radical Smiles rearrangement. However, the eventually formed radical intermediates in these reactions are limited to the amidyl radical, except for the few examples initiated by a N-centered radical. Here, a novel and practical radical Smiles rearrangement triggered by photoredox-catalyzed regioselective ketyl-ynamide coupling is reported, which represents the first radical Smiles rearrangement of ynamides. This method enables facile access to a variety of valuable 2-benzhydrylindoles with broad substrate scope in generally good yields under mild reaction conditions. In addition, this chemistry can also be extended to the divergent synthesis of versatile 3-benzhydrylisoquinolines through a similar ketyl-ynamide coupling and radical Smiles rearrangement, followed by dehydrogenative oxidation. Moreover, such an ynamide Smiles rearrangement initiated by intermolecular photoredox catalysis via addition of external radical sources is also achieved. By control experiments, the reaction was shown to proceed via key ketyl radical and α-imino carbon radical intermediates.

Authors+Show Affiliations

iChEM, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China.iChEM, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China.iChEM, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China.iChEM, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China.School of Chemistry and Chemical Engineering , Jiangsu University , Zhenjiang 212013 , China.iChEM, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China. State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032 , China.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

32003986

Citation

Wang, Ze-Shu, et al. "Ynamide Smiles Rearrangement Triggered By Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines." Journal of the American Chemical Society, vol. 142, no. 7, 2020, pp. 3636-3644.
Wang ZS, Chen YB, Zhang HW, et al. Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines. J Am Chem Soc. 2020;142(7):3636-3644.
Wang, Z. S., Chen, Y. B., Zhang, H. W., Sun, Z., Zhu, C., & Ye, L. W. (2020). Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines. Journal of the American Chemical Society, 142(7), 3636-3644. https://doi.org/10.1021/jacs.9b13975
Wang ZS, et al. Ynamide Smiles Rearrangement Triggered By Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines. J Am Chem Soc. 2020 02 19;142(7):3636-3644. PubMed PMID: 32003986.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines. AU - Wang,Ze-Shu, AU - Chen,Yang-Bo, AU - Zhang,Hao-Wen, AU - Sun,Zhou, AU - Zhu,Chunyin, AU - Ye,Long-Wu, Y1 - 2020/02/10/ PY - 2020/2/1/pubmed PY - 2020/2/1/medline PY - 2020/2/1/entrez SP - 3636 EP - 3644 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 142 IS - 7 N2 - In the past decades, significant advances have been made on radical Smiles rearrangement. However, the eventually formed radical intermediates in these reactions are limited to the amidyl radical, except for the few examples initiated by a N-centered radical. Here, a novel and practical radical Smiles rearrangement triggered by photoredox-catalyzed regioselective ketyl-ynamide coupling is reported, which represents the first radical Smiles rearrangement of ynamides. This method enables facile access to a variety of valuable 2-benzhydrylindoles with broad substrate scope in generally good yields under mild reaction conditions. In addition, this chemistry can also be extended to the divergent synthesis of versatile 3-benzhydrylisoquinolines through a similar ketyl-ynamide coupling and radical Smiles rearrangement, followed by dehydrogenative oxidation. Moreover, such an ynamide Smiles rearrangement initiated by intermolecular photoredox catalysis via addition of external radical sources is also achieved. By control experiments, the reaction was shown to proceed via key ketyl radical and α-imino carbon radical intermediates. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/32003986/Ynamide_Smiles_Rearrangement_Triggered_by_Visible_Light_Mediated_Regioselective_Ketyl_Ynamide_Coupling:_Rapid_Access_to_Functionalized_Indoles_and_Isoquinolines_ L2 - https://doi.org/10.1021/jacs.9b13975 DB - PRIME DP - Unbound Medicine ER -
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