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Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity
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...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162146/ https://www.ncbi.nlm.nih.gov/pubmed/34094279 http://dx.doi.org/10.1039/d0sc03215h |
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author | Huang, Fanping Zheng, Xuejuan Lin, Xinlei Ding, Linting Zhuo, Qingde Wen, Ting Bin Zhang, Hong Xia, Haiping |
author_facet | Huang, Fanping Zheng, Xuejuan Lin, Xinlei Ding, Linting Zhuo, Qingde Wen, Ting Bin Zhang, Hong Xia, Haiping |
author_sort | Huang, Fanping |
collection | PubMed |
description | 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 σ-aromaticity in an unsaturated three-membered ring. The structures of such products are supported by experimental observations and theoretical calculations. |
format | Online Article Text |
id | pubmed-8162146 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81621462021-06-04 Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity Huang, Fanping Zheng, Xuejuan Lin, Xinlei Ding, Linting Zhuo, Qingde Wen, Ting Bin Zhang, Hong Xia, Haiping Chem Sci Chemistry 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 σ-aromaticity in an unsaturated three-membered ring. The structures of such products are supported by experimental observations and theoretical calculations. The Royal Society of Chemistry 2020-09-03 /pmc/articles/PMC8162146/ /pubmed/34094279 http://dx.doi.org/10.1039/d0sc03215h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Huang, Fanping Zheng, Xuejuan Lin, Xinlei Ding, Linting Zhuo, Qingde Wen, Ting Bin Zhang, Hong Xia, Haiping Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
title | Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
title_full | Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
title_fullStr | Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
title_full_unstemmed | Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
title_short | Extension of the Simmons–Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
title_sort | extension of the simmons–smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162146/ https://www.ncbi.nlm.nih.gov/pubmed/34094279 http://dx.doi.org/10.1039/d0sc03215h |
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