Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (07): 1064-1070.DOI: 10.6023/A13030249 Previous Articles     Next Articles



胡锐, 张承平, 裴志胜   

  1. 琼州学院理工学院 三亚 572022
  • 投稿日期:2013-03-07 发布日期:2013-04-10
  • 通讯作者: 胡锐, E-mail:; Tel.: 15120716578
  • 基金资助:

    项目受海南省高等学校科学研究项目(No. HJKJ2011-38)资助.

Mechanistic Investigation of Light-induced Asymmetric Hydrogenation of TMSBO by Anoxygenic Photosynthetic Bacteria

Hu Rui, Zhang Chengping, Pei Zhisheng   

  1. Institute of Technology, Qiongzhou University, Sanya 572022
  • Received:2013-03-07 Published:2013-04-10
  • Supported by:

    Project supported by the Higher School Science Research Project of Hainan Province (No. HJKJ2011-38).

Enantiomerically pure organosilicon compounds 3-butyn-2-ol not only play an important part in asymmetric synthesis and functional materials, but also many of them are bioactive and can be applied as silicon-containing drugs, such as (S)-3-butyn-2-ol or its derivative (S)-4-(trimethylsilyl)-3-butyn-2-ol {(S)-TMSBL} is a crucial intermediate for the synthesis of 5-lipoxygenase inhibitors. The anoxygenic phototrophic bacteria capable of reducing TMSBO to the (S)-TMSBL with high yield and ee were screened, using absolute configuration, stereoselectivity, and yield as benchmarks. 51 anoxygenic phototrophic bacteria strains were tested. We, for the first time, describe the efficient synthesis of enantiopure (S)-TMSBL, which is a crucial intermediate for the synthesis of 5-lipoxygenase inhibitors through the light-controlled asymmetric hydrogenation of TMSBO by photosynthetic bacteria Thiocapsa roseopersicina SJH001, which is a newly isolated photosynthetic bacteria strain that has the capacity to capture light energy and to generate NADPH through photosynthetic electron-transfer reactions. No oxygen or other metabolic intermediates were used, which make it easy to keep higher activities of redoxase and to separate reduced product, the reducing power of NADPH generated through photosynthesis also can be used in the reduction of exogenous substrates. A novel NADPH dependent carbonyl reductase was separated from Thiocapsa roseopersicina SJH001. The enzyme gave a single band on SDS-PAGE, which was purified through ammonium sulfate, Q-sepharose anion exchange column, gel filtration chromatography on a Superdex 200 column from cell-free extract. The molecular mass of the enzyme was about 44.5 kDa, relative enzyme activity was 449.8 U/mg, which is comparable to the previously reported carbonyl reductases from other sources. These results suggested that pH, light intensity, heat-treat biocatalysis with different temperature, substrate concentration has great influence on the enzyme activity and configuration of carbonyl reductase ((S)-carbonyl reductase and (R)-carbonyl reductase) from Thiocapsa roseopersicina SJH001. We propose a probable mechanism for light-induced asymmetric hydrogenation of TMSBO to produce (S)-TMSBL by anoxygenic photosynthetic bacteria.

Key words: light-induced asymmetric hydrogenation, (S)-carbonyl reductase (R)-carbonyl reductase, 4-(trimethylsilyl)-3-butyn-2-one, (S)-4-(trimethylsilyl)-3-butyn-2-ol