2020年3月1日
Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions
Nature Chemistry
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- 巻
- 12
- 号
- 3
- 開始ページ
- 276
- 終了ページ
- 283
- 記述言語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1038/s41557-019-0409-4
© 2020, The Author(s), under exclusive licence to Springer Nature Limited. Anti-Markovnikov additions to alkenes have been a longstanding goal of catalysis, and anti-Markovnikov addition of arenes to alkenes would produce alkylarenes that are distinct from those formed by acid-catalysed processes. Existing hydroarylations are either directed or occur with low reactivity and low regioselectivity for the n-alkylarene. Herein, we report the first undirected hydroarylation of unactivated alkenes with unactivated arenes that occurs with high regioselectivity for the anti-Markovnikov product. The reaction occurs with a nickel catalyst ligated by a highly sterically hindered N-heterocyclic carbene. Catalytically relevant arene- and alkene-bound nickel complexes have been characterized, and the rate-limiting step was shown to be reductive elimination to form the C–C bond. Density functional theory calculations, combined with second-generation absolutely localized molecular orbital energy decomposition analysis, suggest that the difference in activity between catalysts containing large and small carbenes results more from stabilizing intramolecular non-covalent interactions in the secondary coordination sphere than from steric hindrance.
- リンク情報
- ID情報
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- DOI : 10.1038/s41557-019-0409-4
- ISSN : 1755-4330
- eISSN : 1755-4349
- ORCIDのPut Code : 113855151
- PubMed ID : 32042137
- SCOPUS ID : 85079452281