Structural Properties and Stereochemically Distinct Folding Preferences of 4,5-cis and trans-Methano-L-Proline Oligomers: The Shortest Crystalline PPII-Type Helical Proline-Derived Tetramer
Structural Properties and Stereochemically Distinct Folding Preferences of 4,5-cis and trans-Methano-L-Proline Oligomers: The Shortest Crystalline PPII-Type Helical Proline-Derived Tetramer
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DOI：
10.1002/anie.201506208
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发表时间：
2015-11-02
影响因子：
16.6
通讯作者：
Hanessian, Stephen
中科院分区：
文献类型：
--
作者：
Berger, Gilles;Vilchis-Reyes, Miguel;Hanessian, Stephen
通过 X 射线晶体学、圆二色性测量和 DFT 计算揭示了以顺式和反式 4,5-亚甲基-L-脯氨酸酰胺及其低聚物为代表的一系列 L-脯氨酸甲醇系物的合成、结构性质和折叠模式。我们公开了具有聚脯氨酸II螺旋构象的结晶四聚脯氨酸同系物的第一个例子。顺式 4,5-亚甲基-L-脯氨酸低聚物的 PPII 型螺旋排列（溶液和固态）的实验证据得到反映反式酰胺构象 n* 稳定程度的理论计算的支持。
The synthesis, structural properties, and folding patterns of a series of L-proline methanologues represented by cis- and trans-4,5-methano-L-proline amides and their oligomers are reported as revealed by X-ray crystallography, circular dichroism measurements, and DFT calculations. We disclose the first example of a crystalline tetrameric proline congener to exhibit a polyprolineII helical conformation. Experimental evidence of PPII-type helical arrangement (both in solution and in the solid state) of cis-4,5-methano-L-proline oligomers is supported by theoretical calculations reflecting the extent of n* stabilization of the trans-amide conformation.