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Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes.
Angew Chem Int Ed Engl. 2015 Oct 26; 54(44):12968-72.AC

Abstract

The synthesis of isoquinolines by site-selective C-H activation of O-acyl oximes with a Cp*Co(III) catalyst is described. In the presence of this catalyst, the C-H activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co(III) system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh(III) catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C-H activation step under Cp*Co(III) and Cp*Rh(III) catalysis.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Sun B
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan).
Yoshino T
Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-ku, Sapporo 060-0812 (Japan). ACT-C (Japan) Science and Technology Agency (Japan).
Kanai M
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan). kanai@mol.f.u-tokyo.ac.jp.
Matsunaga S
Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-ku, Sapporo 060-0812 (Japan). smatsuna@pharm.hokudai.ac.jp. ACT-C (Japan) Science and Technology Agency (Japan). smatsuna@pharm.hokudai.ac.jp.

MeSH

AlkynesCatalysisCobaltCyclopentanesIsoquinolinesMolecular StructureOrganometallic CompoundsOximes

Pub Type(s)

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

Language

eng

PubMed ID

26412390

Citation

Sun, Bo, et al. "Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines From Terminal and Internal Alkynes." Angewandte Chemie (International Ed. in English), vol. 54, no. 44, 2015, pp. 12968-72.
Sun B, Yoshino T, Kanai M, et al. Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes. Angew Chem Int Ed Engl. 2015;54(44):12968-72.
Sun, B., Yoshino, T., Kanai, M., & Matsunaga, S. (2015). Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes. Angewandte Chemie (International Ed. in English), 54(44), 12968-72. https://doi.org/10.1002/anie.201507744
Sun B, et al. Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines From Terminal and Internal Alkynes. Angew Chem Int Ed Engl. 2015 Oct 26;54(44):12968-72. PubMed PMID: 26412390.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes. AU - Sun,Bo, AU - Yoshino,Tatsuhiko, AU - Kanai,Motomu, AU - Matsunaga,Shigeki, Y1 - 2015/09/28/ PY - 2015/08/19/received PY - 2015/9/29/entrez PY - 2015/9/29/pubmed PY - 2016/4/22/medline KW - CH activation KW - cobalt KW - isoquinolines KW - transition-metal catalysis SP - 12968 EP - 72 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 54 IS - 44 N2 - The synthesis of isoquinolines by site-selective C-H activation of O-acyl oximes with a Cp*Co(III) catalyst is described. In the presence of this catalyst, the C-H activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co(III) system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh(III) catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C-H activation step under Cp*Co(III) and Cp*Rh(III) catalysis. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/26412390/Cp_Co_III__Catalyzed_Site_Selective_C_H_Activation_of_Unsymmetrical_O_Acyl_Oximes:_Synthesis_of_Multisubstituted_Isoquinolines_from_Terminal_and_Internal_Alkynes_ DB - PRIME DP - Unbound Medicine ER -