A Highly Active Biohybrid Catalyst for Olefin Metathesis in Water: Impact of a Hydrophobic Cavity in a 尾-Barrel Protein
详细信息 查看全文
- 作者：Daniel F. Sauer ; Tomoki Himiyama ; Kengo Tachikawa ; Kazuki Fukumoto ; Akira Onoda ; Eiichi Mizohata ; Tsuyoshi Inoue ; Marco Bocola ; Ulrich Schwaneberg ; Takashi Hayashi ; Jun Okuda
- 刊名：ACS Catalysis
- 出版年：2015
- 出版时间：December 4, 2015
- 年：2015
- 卷：5
- 期：12
- 页码：7519-7522
- 全文大小：359K
- ISSN：2155-5435
文摘
A series of Grubbs鈥揌oveyda type catalyst precursors for olefin metathesis containing a maleimide moiety in the backbone of the NHC ligand was covalently incorporated in the cavity of the 尾-barrel protein nitrobindin. By using two protein mutants with different cavity sizes and choosing the suitable spacer length, an artificial metalloenzyme for olefin metathesis reactions in water in the absence of any organic cosolvents was obtained. High efficiencies reaching TON > 9000 in the ROMP of a water-soluble 7-oxanorbornene derivative and TON > 100 in ring-closing metathesis (RCM) of 4,4-bis(hydroxymethyl)-1,6-heptadiene in water under relatively mild conditions (pH 6, T = 25鈥?0 掳C) were observed.