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Divergent synthesis of N-heterocycles via controllable cyclization of azido-diynes catalyzed by copper and gold.
Nat Commun. 2017 11 23; 8(1):1748.NC

Abstract

Gold-catalyzed intermolecular alkyne oxidation by an N-O bond oxidant has proven to be a powerful method in organic synthesis during the past decade, because this approach would enable readily available alkynes as precursors in generating α-oxo gold carbenes. Among those, gold-catalyzed oxidative cyclization of dialkynes has received particular attention as this chemistry offers great potential to build structurally complex cyclic molecules. However, these alkyne oxidations have been mostly limited to noble metal catalysts, and, to our knowledge, non-noble metal-catalyzed reactions such as diyne oxidations have not been reported. Herein, we disclose a copper-catalyzed oxidative diyne cyclization, allowing the facile synthesis of a wide range of valuable pyrrolo[3,4-c]quinolin-1-ones. Interestingly, by employing the same starting materials, the gold-catalyzed cascade cyclization leads to the divergent formation of synthetically useful pyrrolo[2,3-b]indoles. Furthermore, the proposed mechanistic rationale for these cascade reactions is strongly supported by both control experiments and theoretical calculations.

Authors+Show Affiliations

Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. xinlu@xmu.edu.cn.Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. longwuye@xmu.edu.cn. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China. longwuye@xmu.edu.cn.

Pub Type(s)

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

Language

eng

PubMed ID

29170497

Citation

Shen, Wen-Bo, et al. "Divergent Synthesis of N-heterocycles Via Controllable Cyclization of Azido-diynes Catalyzed By Copper and Gold." Nature Communications, vol. 8, no. 1, 2017, p. 1748.
Shen WB, Sun Q, Li L, et al. Divergent synthesis of N-heterocycles via controllable cyclization of azido-diynes catalyzed by copper and gold. Nat Commun. 2017;8(1):1748.
Shen, W. B., Sun, Q., Li, L., Liu, X., Zhou, B., Yan, J. Z., Lu, X., & Ye, L. W. (2017). Divergent synthesis of N-heterocycles via controllable cyclization of azido-diynes catalyzed by copper and gold. Nature Communications, 8(1), 1748. https://doi.org/10.1038/s41467-017-01853-1
Shen WB, et al. Divergent Synthesis of N-heterocycles Via Controllable Cyclization of Azido-diynes Catalyzed By Copper and Gold. Nat Commun. 2017 11 23;8(1):1748. PubMed PMID: 29170497.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Divergent synthesis of N-heterocycles via controllable cyclization of azido-diynes catalyzed by copper and gold. AU - Shen,Wen-Bo, AU - Sun,Qing, AU - Li,Long, AU - Liu,Xin, AU - Zhou,Bo, AU - Yan,Juan-Zhu, AU - Lu,Xin, AU - Ye,Long-Wu, Y1 - 2017/11/23/ PY - 2017/07/19/received PY - 2017/10/19/accepted PY - 2017/11/25/entrez PY - 2017/11/25/pubmed PY - 2017/11/25/medline SP - 1748 EP - 1748 JF - Nature communications JO - Nat Commun VL - 8 IS - 1 N2 - Gold-catalyzed intermolecular alkyne oxidation by an N-O bond oxidant has proven to be a powerful method in organic synthesis during the past decade, because this approach would enable readily available alkynes as precursors in generating α-oxo gold carbenes. Among those, gold-catalyzed oxidative cyclization of dialkynes has received particular attention as this chemistry offers great potential to build structurally complex cyclic molecules. However, these alkyne oxidations have been mostly limited to noble metal catalysts, and, to our knowledge, non-noble metal-catalyzed reactions such as diyne oxidations have not been reported. Herein, we disclose a copper-catalyzed oxidative diyne cyclization, allowing the facile synthesis of a wide range of valuable pyrrolo[3,4-c]quinolin-1-ones. Interestingly, by employing the same starting materials, the gold-catalyzed cascade cyclization leads to the divergent formation of synthetically useful pyrrolo[2,3-b]indoles. Furthermore, the proposed mechanistic rationale for these cascade reactions is strongly supported by both control experiments and theoretical calculations. SN - 2041-1723 UR - https://www.unboundmedicine.com/medline/citation/29170497/Divergent_synthesis_of_N_heterocycles_via_controllable_cyclization_of_azido_diynes_catalyzed_by_copper_and_gold_ L2 - https://doi.org/10.1038/s41467-017-01853-1 DB - PRIME DP - Unbound Medicine ER -
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