Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals

Chu, Zhenwei1,2; Li, Jinhua1,2; Chen, Dafa1,2; Lu, Zhengyu1,2; Meng, Weiran1,2; Luo, Ming1,2; Xia, Haiping1,2

2023-05-01

10.1002/cjoc.202300116

CHINESE JOURNAL OF CHEMISTRY   影响因子和分区

1001-604X

1614-7065

Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes. Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed, [2+1] cycloadditions of metallacyclopentadienes and alkynes have never been discovered. In present work, we report the formal [2+1] cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes, providing a facile strategy to construct tetracyclic conjugated compounds. The deuterated experiment indicates a metal vinylidene intermediate has been involved in [2+1] cycloaddition. Moreover, the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory (DFT) calculated Fukui functions is investigated. These tetracyclic conjugated compounds exhibit broad absorption spectra in the whole visible region which could be employed as potential photovoltaic materials.

Metallacycle Cycloaddition Alkynes Electrophilic substitution Conjugation

SCI

英语

第一 ; 通讯

National Natural Science Foundation of China["21931002","22071098","22101115","22101123"] ; Shenzhen Science and Technology Innovation Committee["JCYJ20200109140812302","JCYJ20210324105013035"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000988345400001

WILEY-V C H VERLAG GMBH

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China

Chu, Zhenwei,Li, Jinhua,Chen, Dafa,et al. Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals[J]. CHINESE JOURNAL OF CHEMISTRY,2023,41(16).

Chu, Zhenwei.,Li, Jinhua.,Chen, Dafa.,Lu, Zhengyu.,Meng, Weiran.,...&Xia, Haiping.(2023).Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals.CHINESE JOURNAL OF CHEMISTRY,41(16).

Chu, Zhenwei,et al."Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals".CHINESE JOURNAL OF CHEMISTRY 41.16(2023).