Catalysis with phosphine-containing amino acids in various "turn" motifs
Catalysis with phosphine-containing amino acids in various "turn" motifs
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DOI：
10.1021/jo049103g
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发表时间：
2004-11-12
影响因子：
3.6
通讯作者：
Gilbertson, SR
中科院分区：
文献类型：
--
作者：
Agarkov, A;Greenfield, SJ;Gilbertson, SR
我们一直积极参与发现膦配体的平行方法的开发。我们的方法是基于将含膦的氨基酸掺入到被设计为具有稳定二级结构的肽序列中。我们已经研究了螺旋和转弯的二级结构，并报道了环戊烯基乙酸酯与丙二酸二甲酯的烷基化反应可以在高对映体过量（ee）下用β-转弯配体催化。肽二级结构的重要性通过一系列肽配体的合成得到证明，其中转角形成残基的性质被探测。此外，已经检查了其他转角形成单元和各种不同的含膦氨基酸控制烯丙基化反应选择性的能力。本文报道了通过对“最佳”转角序列Pps-Pro-D-Xxx-Pps上的不同转角基序以及不同膦取代的检查所获得的结果。
We have been actively involved in the development of parallel approaches for the discovery of phosphine ligands. Our approach has been based on the incorporation of phosphine-containing amino acids into peptide sequences that are designed to have stable secondary structures. We have examined helical and turn secondary structures and have reported that alkylation of cyclopentenyl acetate with dimethylmalonate can be catalyzed in high enantiomeric excess (ee) with a beta-turn-based ligand. The importance of the peptide secondary structure was demonstrated through the synthesis of a series of peptide ligands where the nature of the turn-forming residues was probed. Additionally, other turn-forming units and a variety of different phosphine-containing amino acids have been examined for their ability to control the selectivity of the allylation reaction. This paper reports the results obtained through the examination of different turn motifs as well as different phosphine substitutions on the "best" turn sequence, Pps-Pro-D-Xxx-Pps.