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Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons.
Angew Chem Int Ed Engl. 2019 07 08; 58(28):9632-9639.AC

Abstract

Catalytic cycloisomerization-initiated cascade cyclizations of terminal alkynes have received tremendous interest, and been widely used in the facile synthesis of a diverse array of valuable complex heterocycles. However, these tandem reactions have been mostly limited to noble-metal catalysis, and are initiated by an exo-cyclization pathway. Reported herein is an unprecedented copper-catalyzed endo-cyclization-initiated tandem reaction of indolyl homopropargyl amides, where copper catalyzes both the hydroamination and Friedel-Crafts alkylation process. This method allows the practical and atom-economical synthesis of valuable bridged aza-[n.2.1] skeletons (n=3-6) with wide substrate scope, and excellent diastereoselectivity and enantioselectivity by a chirality-transfer strategy. Moreover, the mechanistic rationale for this novel cascade cyclization is also strongly supported by control experiments, and is distinctively different from the related gold catalysis.

Authors+Show Affiliations

State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory for 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 for 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 for 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 for 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 for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, China.

Pub Type(s)

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

Language

eng

PubMed ID

31095848

Citation

Tan, Tong-De, et al. "Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons." Angewandte Chemie (International Ed. in English), vol. 58, no. 28, 2019, pp. 9632-9639.
Tan TD, Zhu XQ, Bu HZ, et al. Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons. Angew Chem Int Ed Engl. 2019;58(28):9632-9639.
Tan, T. D., Zhu, X. Q., Bu, H. Z., Deng, G., Chen, Y. B., Liu, R. S., & Ye, L. W. (2019). Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons. Angewandte Chemie (International Ed. in English), 58(28), 9632-9639. https://doi.org/10.1002/anie.201904698
Tan TD, et al. Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons. Angew Chem Int Ed Engl. 2019 07 8;58(28):9632-9639. PubMed PMID: 31095848.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons. AU - Tan,Tong-De, AU - Zhu,Xin-Qi, AU - Bu,Hao-Zhen, AU - Deng,Guocheng, AU - Chen,Yang-Bo, AU - Liu,Rai-Shung, AU - Ye,Long-Wu, Y1 - 2019/06/06/ PY - 2019/04/16/received PY - 2019/5/17/pubmed PY - 2019/5/17/medline PY - 2019/5/17/entrez KW - copper KW - cyclizations KW - heterocycles KW - stereoselectivity KW - synthetic methods SP - 9632 EP - 9639 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 58 IS - 28 N2 - Catalytic cycloisomerization-initiated cascade cyclizations of terminal alkynes have received tremendous interest, and been widely used in the facile synthesis of a diverse array of valuable complex heterocycles. However, these tandem reactions have been mostly limited to noble-metal catalysis, and are initiated by an exo-cyclization pathway. Reported herein is an unprecedented copper-catalyzed endo-cyclization-initiated tandem reaction of indolyl homopropargyl amides, where copper catalyzes both the hydroamination and Friedel-Crafts alkylation process. This method allows the practical and atom-economical synthesis of valuable bridged aza-[n.2.1] skeletons (n=3-6) with wide substrate scope, and excellent diastereoselectivity and enantioselectivity by a chirality-transfer strategy. Moreover, the mechanistic rationale for this novel cascade cyclization is also strongly supported by control experiments, and is distinctively different from the related gold catalysis. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/31095848/Copper_Catalyzed_Cascade_Cyclization_of_Indolyl_Homopropargyl_Amides:_Stereospecific_Construction_of_Bridged_Aza_[n_2_1]_Skeletons_ L2 - https://doi.org/10.1002/anie.201904698 DB - PRIME DP - Unbound Medicine ER -
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