Ring contraction of metallacyclobutadiene to metallacyclopropene driven by π- and σ-aromaticity relay

Zhuo，Kaiyue1; Liu，Yanan1; Ruan，Kaidong1; Hua，Yuhui2; Lin，Yu Mei1; Xia，Haiping1,2

2023

10.1038/s44160-022-00194-2

Nature Synthesis   Impact Factor & Quartile

2731-0582

π-Aromaticity is an important driving force in directing the synthesis of aromatic compounds; in contrast, reactions induced by σ-aromaticity are uncommon. Here we report a strategy based on π- and σ-aromaticity relays to realize the structurally defined ring contraction of metallacyclobutadiene to metallacyclopropene. This reaction involves the release of the π-antiaromaticity of metallacyclobutadiene to afford a π-aromatic intermediate, followed by ring reclosure to generate σ-aromatic metallacyclopropene. The ring opening–reclosing mechanism and versatile switching of the aromaticity of the metallacyclic species are supported by experimental results and theoretical calculations. This work demonstrates the importance of aromaticity relay with the successive decrease of energy in reactions and will stimulate efforts in exploiting the vital role of aromaticity in synthetic chemistry. [Figure not available: see fulltext.]

SCI

English

Corresponding

Natural Science Foundation of Fujian Province[2020J01025];National Natural Science Foundation of China-Yunnan Joint Fund[21931002];National Natural Science Foundation of China-Yunnan Joint Fund[22071206];National Natural Science Foundation of China-Yunnan Joint Fund[92156021];Science, Technology and Innovation Commission of Shenzhen Municipality[JCYJ20200109140812302];

WOS:000982855600019

2-s2.0-85152218494

Scopus

1.State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,China
2.Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen,China

Zhuo，Kaiyue,Liu，Yanan,Ruan，Kaidong,et al. Ring contraction of metallacyclobutadiene to metallacyclopropene driven by π- and σ-aromaticity relay[J]. Nature Synthesis,2023,2(1):67-75.

Zhuo，Kaiyue,Liu，Yanan,Ruan，Kaidong,Hua，Yuhui,Lin，Yu Mei,&Xia，Haiping.(2023).Ring contraction of metallacyclobutadiene to metallacyclopropene driven by π- and σ-aromaticity relay.Nature Synthesis,2(1),67-75.

Zhuo，Kaiyue,et al."Ring contraction of metallacyclobutadiene to metallacyclopropene driven by π- and σ-aromaticity relay".Nature Synthesis 2.1(2023):67-75.