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Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles.
J Am Chem Soc. 2019 10 23; 141(42):16961-16970.JA

Abstract

The generation of metal carbenes from readily available alkynes represents a significant advance in metal carbene chemistry. However, most of these transformations are based on the use of noble-metal catalysts and successful examples of such an asymmetric version are still very scarce. Here a copper-catalyzed enantioselective cascade cyclization of N-propargyl ynamides is reported, enabling the practical and atom-economical construction of diverse chiral polycyclic pyrroles in generally good to excellent yields with wide substrate scope and excellent enantioselectivities (up to 97:3 e.r.). Importantly, this protocol represents the first copper-catalyzed asymmetric diyne cyclization. Moreover, mechanistic studies revealed that the generation of donor/donor copper carbenes is presumably involved in this 1,5-diyne cyclization, which is distinctively different from the related gold catalysis, and thus it constitutes a novel way for the generation of donor/donor metal carbenes.

Authors+Show Affiliations

State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and 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, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and 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, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and 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, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and 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, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and 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, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , 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, Key Laboratory for Theoretical and Computational Chemistry 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

31557018

Citation

Hong, Feng-Lin, et al. "Generation of Donor/Donor Copper Carbenes Through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles." Journal of the American Chemical Society, vol. 141, no. 42, 2019, pp. 16961-16970.
Hong FL, Wang ZS, Wei DD, et al. Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles. J Am Chem Soc. 2019;141(42):16961-16970.
Hong, F. L., Wang, Z. S., Wei, D. D., Zhai, T. Y., Deng, G. C., Lu, X., Liu, R. S., & Ye, L. W. (2019). Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles. Journal of the American Chemical Society, 141(42), 16961-16970. https://doi.org/10.1021/jacs.9b09303
Hong FL, et al. Generation of Donor/Donor Copper Carbenes Through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles. J Am Chem Soc. 2019 10 23;141(42):16961-16970. PubMed PMID: 31557018.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles. AU - Hong,Feng-Lin, AU - Wang,Ze-Shu, AU - Wei,Dong-Dong, AU - Zhai,Tong-Yi, AU - Deng,Guo-Cheng, AU - Lu,Xin, AU - Liu,Rai-Shung, AU - Ye,Long-Wu, Y1 - 2019/10/09/ PY - 2019/9/27/pubmed PY - 2019/9/27/medline PY - 2019/9/27/entrez SP - 16961 EP - 16970 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 141 IS - 42 N2 - The generation of metal carbenes from readily available alkynes represents a significant advance in metal carbene chemistry. However, most of these transformations are based on the use of noble-metal catalysts and successful examples of such an asymmetric version are still very scarce. Here a copper-catalyzed enantioselective cascade cyclization of N-propargyl ynamides is reported, enabling the practical and atom-economical construction of diverse chiral polycyclic pyrroles in generally good to excellent yields with wide substrate scope and excellent enantioselectivities (up to 97:3 e.r.). Importantly, this protocol represents the first copper-catalyzed asymmetric diyne cyclization. Moreover, mechanistic studies revealed that the generation of donor/donor copper carbenes is presumably involved in this 1,5-diyne cyclization, which is distinctively different from the related gold catalysis, and thus it constitutes a novel way for the generation of donor/donor metal carbenes. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/31557018/Generation_of_Donor/Donor_Copper_Carbenes_through_Copper_Catalyzed_Diyne_Cyclization:_Enantioselective_and_Divergent_Synthesis_of_Chiral_Polycyclic_Pyrroles_ L2 - https://doi.org/10.1021/jacs.9b09303 DB - PRIME DP - Unbound Medicine ER -
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