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Copper-Catalyzed Azide-Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles.
Angew Chem Int Ed Engl. 2020 Oct 05; 59(41):17984-17990.AC

Abstract

Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide-ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide-alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations.

Authors+Show Affiliations

State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing, 210095, China.Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan, 30013, Republic of China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, 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

Language

eng

PubMed ID

32621338

Citation

Liu, Xin, et al. "Copper-Catalyzed Azide-Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles." Angewandte Chemie (International Ed. in English), vol. 59, no. 41, 2020, pp. 17984-17990.
Liu X, Wang ZS, Zhai TY, et al. Copper-Catalyzed Azide-Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles. Angew Chem Int Ed Engl. 2020;59(41):17984-17990.
Liu, X., Wang, Z. S., Zhai, T. Y., Luo, C., Zhang, Y. P., Chen, Y. B., Deng, C., Liu, R. S., & Ye, L. W. (2020). Copper-Catalyzed Azide-Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles. Angewandte Chemie (International Ed. in English), 59(41), 17984-17990. https://doi.org/10.1002/anie.202007206
Liu X, et al. Copper-Catalyzed Azide-Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles. Angew Chem Int Ed Engl. 2020 Oct 5;59(41):17984-17990. PubMed PMID: 32621338.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Copper-Catalyzed Azide-Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles. AU - Liu,Xin, AU - Wang,Ze-Shu, AU - Zhai,Tong-Yi, AU - Luo,Chen, AU - Zhang,Yi-Ping, AU - Chen,Yang-Bo, AU - Deng,Chao, AU - Liu,Rai-Shung, AU - Ye,Long-Wu, Y1 - 2020/08/17/ PY - 2020/05/18/received PY - 2020/06/11/revised PY - 2020/7/6/pubmed PY - 2020/7/6/medline PY - 2020/7/5/entrez KW - alkynes KW - asymmetric catalysis KW - copper KW - cyclizations KW - heterocycles SP - 17984 EP - 17990 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 59 IS - 41 N2 - Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide-ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide-alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/32621338/Copper_Catalyzed_Azide_Ynamide_Cyclization_to_Generate_��_Imino_Copper_Carbenes:_Divergent_and_Enantioselective_Access_to_Polycyclic_N_Heterocycles_ DB - PRIME DP - Unbound Medicine ER -
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