Carbolong Chemistry: Planar CCCCX-Type (X = N, O, S) Pentadentate Chelates by Formal [3+1] Cycloadditions of Metalla-Azirines with Terminal Alkynes.

Ming Luo1; Yuhui Hua1; Kaiyue Zhuo1; Lipeng Long1; Xinlei Lin1; Zhihong Deng1; Zhenyang Lin2; Hong Zhang1; Dafa Chen3; Haiping Xia1,3

2020-05-29

10.31635/ccschem.020.202000223

CCS Chem. 2   影响因子和分区

2096-5745

Three-membered unsaturated rings have been widely utilized in organic synthesis due to their inherent highly strained structures. Although much research has been applied to ring-expansion reactions of such strained ring systems, pathways other than [3+2] cycloadditions have rarely been observed in their reactions with alkynes, and to date, no [3+1] cycloadditions of isolated three-membered unsaturated rings with alkynes have been reported. Here we demonstrate an unprecedented [3+1] cycloaddition in which a fused metalla-azirine is used as a template to generate a series of planar CCCCX-type (X = N, O, S) pentadentate carbolong complexes 3-6. A series of substituted alkynes was tested for further exploration of the scope and mechanism for the [3+1] cycloaddition reactions. Complexes 3-6 represent rare examples of planar pentadentate complexes that assemble four p-conjugated fused rings by one bridgehead atom. These novel complexes are thermally stable in air and absorb ultraviolet, visible, and near-infrared light, and thus are potentially applicable in photoelectric devices and pharmaceuticals.

[3+1] cycloaddition reaction DFT calculations metallacycles strained rings planar pentadentate chelates carbolong complexes

ESCI

英语

通讯

National Natural Science Foundation of China["U1705254",21871225,21931002] ; Fundamental Research Funds for the Central Universities[20720190042] ; Research Grants Council of Hong Kong[N_HKUST603/15]

Chemistry

Chemistry, Multidisciplinary

WOS:000794136000006

CHINESE CHEMICAL SOC

人工提交

1.College of Chemistry and Chemical Engineering, Xiamen University, Xiamen Fujian Province, (China),
2.Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong (China),
3.Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong Province (China)

Ming Luo,Yuhui Hua,Kaiyue Zhuo,等. Carbolong Chemistry: Planar CCCCX-Type (X = N, O, S) Pentadentate Chelates by Formal [3+1] Cycloadditions of Metalla-Azirines with Terminal Alkynes.[J]. CCS Chem. 2,2020,3(2).

Ming Luo.,Yuhui Hua.,Kaiyue Zhuo.,Lipeng Long.,Xinlei Lin.,...&Haiping Xia.(2020).Carbolong Chemistry: Planar CCCCX-Type (X = N, O, S) Pentadentate Chelates by Formal [3+1] Cycloadditions of Metalla-Azirines with Terminal Alkynes..CCS Chem. 2,3(2).

Ming Luo,et al."Carbolong Chemistry: Planar CCCCX-Type (X = N, O, S) Pentadentate Chelates by Formal [3+1] Cycloadditions of Metalla-Azirines with Terminal Alkynes.".CCS Chem. 2 3.2(2020).