α-シリル有機アルキル金属錯体のユニークな反応性の発見～アルカリ金属錯体の新たな設計指針へ～

2026-04-23 北海道大学

α-シリル有機アルカリ金属錯体の新しい反応を見出すことに成功

＜関連情報＞

• https://www.hokudai.ac.jp/news/2026/04/–12.html
• https://www.hokudai.ac.jp/news/pdf/260423_pr.pdf
• https://onlinelibrary.wiley.com/doi/10.1002/anie.8906317

単核α-シリル有機リチウム／ナトリウム錯体における金属-炭素結合と炭素-シリコン結合の逐次的反応性：CO、CO2及びヘテロアレン類との反応 Tandem Reactivity of Metal−Carbon and Carbon−Silicon Bonds in Mononuclear α-Silyl Organolithium or Organosodium Complexes Towards CO, CO2 and Heteroallenes

Xiao Yang, Jack M. Hemingway, Wataru Kanna, Nathan Davison, Hiroki Hayashi, Louise Male, Paul G. Waddell, James A. Dawson, Erli Lu
Angewandte Chemie International Edition  Published:published: 11 April 2026
DOI:https://doi.org/10.1002/anie.8906317

ABSTRACT

α-Silyl alkyl complexes, such as the ubiquitous MCH₂SiMe₃, are some of the most used organometallic building blocks and reagents. Hitherto, most reports focus on the reactive metal–carbon bond, while the carbon–silicon bond has thus far been limited to a handful of serendipitous reaction patterns. Herein, by examining a range of reactions between mononuclear Li or Na α-silyl alkyl complexes and CO, CO₂, or heteroallenes (isocyanates, isothiocyanates, carbodiimides), we report tandem M─C and C─Si bond reactivity, with in-depth mechanistic understanding unveiled by computational reaction pathway studies enabled by the artificial force induced reaction (AFIR) method. By bringing the long-neglected C─Si bond reactivity to the awareness of synthetic chemists, we demonstrate that the C─Si bond should be taken into account in reaction design when using these α-silyl alkyl complexes.