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Rhodium(iii)-catalyzed diverse [4 + 1] annulation of arenes with 1,3-enynes via sp3/sp2 C-H activation and 1,4-rhodium migration.
Chem Sci. 2019 Apr 14; 10(14):3987-3993.CS

Abstract

Nitrogen-rich heterocyclic compounds have a profound impact on human health. Despite the numerous synthetic methods, diversified, step-economic, and general synthesis of heterocycles remains limited. C-H bond functionalization catalyzed by rhodium(iii) cyclopentadienyls has proven to be a powerful strategy in the synthesis of diversified heterocycles. Herein we describe rhodium(iii)-catalyzed sp2 and sp3 C-H activation-oxidative annulations between aromatic substrates and 1,3-enynes, where alkenyl-to-allyl 1,4-rhodium(iii) migration enabled the generation of electrophilic rhodium(iii) π-allyls via remote C-H functionalization. Subsequent nucleophilic trapping of these species by various sp2-hybridized N-nucleophiles delivered three classes (external salts, inner salts, and neutral azacycles) of five-membered azacycles bearing a tetrasubstituted saturated carbon center, as a result of [4 + 1] annulation with the alkyne being a one-carbon synthon. All the reactions proceeded under relatively mild conditions with broad substrate scope, high efficiency, and excellent regioselectivity. The synthetic applications of this protocol have also been demonstrated, and experimental studies have been performed to support the proposed mechanism.

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Authors+Show Affiliations

Henan Key Laboratory of Organic Functional Molecule and Drug Innovation , School of Chemistry and Chemical Engineering , Henan Normal University , Xinxiang 453007 , China.

Dalian Institute of Chemical Physics , Chinese Academy of Sciences , Dalian 116023 , China . Email: xwli@dicp.ac.cn. University of Chinese Academy of Sciences , Beijing 100049 , China.

Henan Key Laboratory of Organic Functional Molecule and Drug Innovation , School of Chemistry and Chemical Engineering , Henan Normal University , Xinxiang 453007 , China.

Henan Key Laboratory of Organic Functional Molecule and Drug Innovation , School of Chemistry and Chemical Engineering , Henan Normal University , Xinxiang 453007 , China.

Henan Key Laboratory of Organic Functional Molecule and Drug Innovation , School of Chemistry and Chemical Engineering , Henan Normal University , Xinxiang 453007 , China.

Henan Key Laboratory of Organic Functional Molecule and Drug Innovation , School of Chemistry and Chemical Engineering , Henan Normal University , Xinxiang 453007 , China.

School of Chemistry and Chemical Engineering , Shaanxi Normal University (SNNU) , Xi'an 710062 , China . Email: sunjq295@nenu.edu.cn.

Dalian Institute of Chemical Physics , Chinese Academy of Sciences , Dalian 116023 , China . Email: xwli@dicp.ac.cn.

School of Chemistry and Chemical Engineering , Shaanxi Normal University (SNNU) , Xi'an 710062 , China . Email: sunjq295@nenu.edu.cn.

Henan Key Laboratory of Organic Functional Molecule and Drug Innovation , School of Chemistry and Chemical Engineering , Henan Normal University , Xinxiang 453007 , China. Dalian Institute of Chemical Physics , Chinese Academy of Sciences , Dalian 116023 , China . Email: xwli@dicp.ac.cn. School of Chemistry and Chemical Engineering , Shaanxi Normal University (SNNU) , Xi'an 710062 , China . Email: sunjq295@nenu.edu.cn.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31015939

Citation

Bai, Dachang, et al. "Rhodium(iii)-catalyzed Diverse [4 + 1] Annulation of Arenes With 1,3-enynes Via Sp3/sp2 C-H Activation and 1,4-rhodium Migration." Chemical Science, vol. 10, no. 14, 2019, pp. 3987-3993.

Bai D, Xia J, Song F, et al. Rhodium(iii)-catalyzed diverse [4 + 1] annulation of arenes with 1,3-enynes via sp3/sp2 C-H activation and 1,4-rhodium migration. Chem Sci. 2019;10(14):3987-3993.

Bai, D., Xia, J., Song, F., Li, X., Liu, B., Liu, L., Zheng, G., Yang, X., Sun, J., & Li, X. (2019). Rhodium(iii)-catalyzed diverse [4 + 1] annulation of arenes with 1,3-enynes via sp3/sp2 C-H activation and 1,4-rhodium migration. Chemical Science, 10(14), 3987-3993. https://doi.org/10.1039/c9sc00545e

Bai D, et al. Rhodium(iii)-catalyzed Diverse [4 + 1] Annulation of Arenes With 1,3-enynes Via Sp3/sp2 C-H Activation and 1,4-rhodium Migration. Chem Sci. 2019 Apr 14;10(14):3987-3993. PubMed PMID: 31015939.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Rhodium(iii)-catalyzed diverse [4 + 1] annulation of arenes with 1,3-enynes via sp3/sp2 C-H activation and 1,4-rhodium migration. AU - Bai,Dachang, AU - Xia,Jintao, AU - Song,Fangfang, AU - Li,Xueyan, AU - Liu,Bingxian, AU - Liu,Lihong, AU - Zheng,Guangfan, AU - Yang,Xifa, AU - Sun,Jiaqiong, AU - Li,Xingwei, Y1 - 2019/02/26/ PY - 2019/01/30/received PY - 2019/02/21/accepted PY - 2019/4/25/entrez PY - 2019/4/25/pubmed PY - 2019/4/25/medline SP - 3987 EP - 3993 JF - Chemical science JO - Chem Sci VL - 10 IS - 14 N2 - Nitrogen-rich heterocyclic compounds have a profound impact on human health. Despite the numerous synthetic methods, diversified, step-economic, and general synthesis of heterocycles remains limited. C-H bond functionalization catalyzed by rhodium(iii) cyclopentadienyls has proven to be a powerful strategy in the synthesis of diversified heterocycles. Herein we describe rhodium(iii)-catalyzed sp2 and sp3 C-H activation-oxidative annulations between aromatic substrates and 1,3-enynes, where alkenyl-to-allyl 1,4-rhodium(iii) migration enabled the generation of electrophilic rhodium(iii) π-allyls via remote C-H functionalization. Subsequent nucleophilic trapping of these species by various sp2-hybridized N-nucleophiles delivered three classes (external salts, inner salts, and neutral azacycles) of five-membered azacycles bearing a tetrasubstituted saturated carbon center, as a result of [4 + 1] annulation with the alkyne being a one-carbon synthon. All the reactions proceeded under relatively mild conditions with broad substrate scope, high efficiency, and excellent regioselectivity. The synthetic applications of this protocol have also been demonstrated, and experimental studies have been performed to support the proposed mechanism. SN - 2041-6520 UR - https://www.unboundmedicine.com/medline/citation/31015939/Rhodium_iii__catalyzed_diverse_[4_+_1]_annulation_of_arenes_with_13_enynes_via_sp3/sp2_C_H_activation_and_14_rhodium_migration_ DB - PRIME DP - Unbound Medicine ER -