Metallopeptides for Asymmetric Dirhodium Catalysis

被引:115
作者
Sambasivan, Ramya [1 ]
Ball, Zachary T. [1 ]
机构
[1] Rice Univ, Dept Chem, Houston, TX 77251 USA
关键词
SI-H BOND; ARTIFICIAL METALLOENZYMES; CARBENE INSERTION; ACIDS; TECHNOLOGY; ALDEHYDES; PEPTIDES; PROTEIN;
D O I
10.1021/ja103747h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Natural peptide sequences ligate to dirhodium centers through two bridging aspartate side chains, creating a macromolecular ligand framework with helical structure. The generation of a small peptide library allowed optimization of peptide sequence and produced an efficient catalyst for enantioselective carbenoid insertion into Si-H bonds. Analysis of the library indicates that the i-1 and i+3 positions of nonapeptides have the most significant effect on enantioselectivity, though the structural basis for selectivity is different at each of the positions.
引用
收藏
页码:9289 / 9291
页数:3
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