Extension of the Simmons-Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with sigma-aromaticity

Huang, Fanping1,2; Zheng, Xuejuan1,2; Lin, Xinlei1,2; Ding, Linting1,2; Zhuo, Qingde1,2; Wen, Ting Bin1,2; Zhang, Hong1,2; Xia, Haiping1,2,3

2020-10-07

10.1039/d0sc03215h

Chemical Science   影响因子和分区

2041-6520

2041-6539

The Simmons-Smith reaction offers a direct route for conversion of an alkene into a cyclopropane with a zinc carbenoid as the active intermediate. Zinc carbenoids, however, have never delivered a methylene unit to substrates with metal-carbon multiple bonds. Herein, we describe this type of reaction and the construction of three-membered rings has now been applied in organometallic systems by combining classical zinc carbenoid reagents with a range of structurally and electronically diverse metal carbynes. A variety of metallacyclopropene derivatives prepared in this way represent rare examples with sigma-aromaticity in an unsaturated three-membered ring. The structures of such products are supported by experimental observations and theoretical calculations.

SCI ; EI

英语

NI论文

通讯

National Natural Science Foundation of China[U1705254][21871225][21931002] ; Fundamental Research Funds for the Central Universities[20720190042]

Chemistry

Chemistry, Multidisciplinary

WOS:000573713500012

ROYAL SOC CHEMISTRY

20204109336716

Zinc ; Reaction intermediates

Zinc and Alloys:546.3 ; Chemical Products Generally:804 ; Organic Compounds:804.1

Web of Science

1.Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China
2.Xiamen Univ, Coll Chem & Chem Engn, Collaborat Innovat Ctr Chem Energy Mat iChEM, Xiamen 361005, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China

Huang, Fanping,Zheng, Xuejuan,Lin, Xinlei,et al. Extension of the Simmons-Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with sigma-aromaticity[J]. Chemical Science,2020,11(37):10159-10166.

Huang, Fanping.,Zheng, Xuejuan.,Lin, Xinlei.,Ding, Linting.,Zhuo, Qingde.,...&Xia, Haiping.(2020).Extension of the Simmons-Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with sigma-aromaticity.Chemical Science,11(37),10159-10166.

Huang, Fanping,et al."Extension of the Simmons-Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with sigma-aromaticity".Chemical Science 11.37(2020):10159-10166.