Serine-containing 10-membered cyclodepsipeptides. Synthesis and molecular structure of PhCH2CO-DSer-Pro-Pro- and PhCH2CO-DSer-Pro-DPro-.

S Cerrini, E Gavuzzo, G Luisi, F Pinnen
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Abstract

As a part of a research program aimed at studying synthesis and conformation of small ring peptides, the cyclization of diastereoisomeric N-phenylacetyl-seryl-propyl-proline tripeptides has been examined. Two 10-membered peptide lactones, PhCH2CO-DSer-Pro-Pro- 5a and PhCH2CO-DSer-Pro-DPro- 5b, have been isolated by treating the corresponding linear p-nitrophenyl esters with DBU in dry benzene. In these two compounds the serine lactone fragment (a common structural feature of several bioactive cyclodepsipeptides) is inserted into a highly strained small ring system. The conformation in the crystal of 5a and 5b has been studied by X-ray analysis. Both the 10-membered rings of 5a and 5b adopt an overall cis-cis-trans conformation in which the lactone junction is trans. The deviations from planarity of the peptide units vary from delta omega = 30 degrees for the DSer-Pro bond in 5b to delta omega = 5-6 degrees for the DSer-Pro bond in 5a and Pro-DPro bond in 5b. The skeletal atoms of 5b, containing the Pro-DPro sequence, are related by a pseudo-symmetry mirror plane passing through the Pro carbonyl and the opposite DSer C beta H2 group. In both the molecules the exocyclic amide bond adopts an extended conformation with respect to the DSer-Pro ring junction; this arrangement gives rise to a C5-type ring structure which is well evidenced in the case of 5a.

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含丝氨酸的10元环沉积肽。phch2co - dser - pro -和PhCH2CO-DSer-Pro-DPro-的合成及分子结构。
作为研究小环肽合成和构象的研究项目的一部分,研究了非对映异构体n -苯基乙酰-seryl-丙基脯氨酸三肽的环化。用DBU在干苯中处理相应的线性对硝基苯酯,分离得到两个10元肽内酯PhCH2CO-DSer-Pro-Pro- 5a和PhCH2CO-DSer-Pro-DPro- 5b。在这两种化合物中,丝氨酸内酯片段(几种生物活性环沉积肽的共同结构特征)插入到高度紧张的小环系统中。用x射线分析研究了5a和5b晶体的构象。5a和5b的10元环均为整体顺-顺-反式构象,内酯连接为反式。肽单元与平面度的偏差从5b中DSer-Pro键的δ ω = 30度到5b中DSer-Pro键和Pro-DPro键的δ ω = 5-6度不等。含有Pro- dpro序列的5b的骨架原子是通过一个穿过Pro羰基和相反的DSer C β H2基团的伪对称镜像面连接起来的。在这两种分子中,外环酰胺键相对于DSer-Pro环结采用延伸构象;这种排列产生了c5型环状结构,这在5a的例子中得到了很好的证明。
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