Macrocylases as synthetic tools for ligand synthesis: enzymatic synthesis of cyclic peptides containing metal-binding amino acids.
Macrocylases as synthetic tools for ligand synthesis: enzymatic synthesis of cyclic peptides containing metal-binding amino acids.
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DOI：
10.1098/rsos.211098
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发表时间：
2021-11
影响因子：
3.5
通讯作者：
Jarvis AG
中科院分区：
文献类型：
--
作者：
Brewster RC;Labeaga IC;Soden CE;Jarvis AG
提高合成的可持续性是绿色化学的一个主要目标，不对称过渡金属催化的发展极大地帮助了这一目标。不对称催化的最新进展表明，控制底物配位范围的能力可以导致对映选择性和活性的改善，类似于酶的操作方式。肽可以用来模拟酶的结构和它们的二级相互作用，它们很容易通过固相肽合成。尽管如此，由于大环化后的合成复杂性，环肽作为手性配体用于催化仍然探索不足。在这里，我们表明，固相合成的肽含有金属结合氨基酸，联吡啶丙氨酸（1），苯基吡啶丙氨酸（2）和N，N-二甲基组氨酸（3）可以结合肽大环化使用肽环化酶1（PCY 1），在温和的条件下产生环肽。观察到线性肽的高转化率（约10%）。在吲哚的Friedel-Crafts/共轭加成反应中，Cu键合的环（FSAS（1）SSKP）是一种有效的催化剂。这项研究表明，PCY 1可以耐受含有经典无机和有机金属配体作为侧链的氨基酸的肽，为环肽作为金属配体的流线型和高效开发打开了大门。
Improving the sustainability of synthesis is a major goal in green chemistry, which has been greatly aided by the development of asymmetric transition metal catalysis. Recent advances in asymmetric catalysis show that the ability to control the coordination sphere of substrates can lead to improvements in enantioselectivity and activity, in a manner resembling the operation of enzymes. Peptides can be used to mimic enzyme structures and their secondary interactions and they are easily accessible through solid-phase peptide synthesis. Despite this, cyclic peptides remain underexplored as chiral ligands for catalysis due to synthetic complications upon macrocyclization. Here, we show that the solid-phase synthesis of peptides containing metal-binding amino acids, bipyridylalanine (1), phenyl pyridylalanine (2) and N,N-dimethylhistidine (3) can be combined with peptide macrocylization using peptide cyclase 1 (PCY1) to yield cyclic peptides under mild conditions. High conversions of the linear peptides were observed (approx. 90%) and the Cu-bound cyclo(FSAS(1)SSKP) was shown to be a competent catalyst in the Friedel-Crafts/conjugate addition of indole. This study shows that PCY1 can tolerate peptides containing amino acids with classic inorganic and organometallic ligands as side chains, opening the door to the streamlined and efficient development of cyclic peptides as metal ligands.
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影响因子：
15
作者：
Metrano AJ;Abascal NC;Mercado BQ;Paulson EK;Hurtley AE;Miller SJ
通讯作者：
Miller SJ
DOI：
10.1039/d1cc03158a
发表时间：
2021-09-09
期刊：
Chemical communications (Cambridge, England)
影响因子：
--
作者：
Lenzen K;Planchestainer M;Feller I;Padrosa DR;Paradisi F;Albrecht M
通讯作者：
Albrecht M
影响因子：
16.8
作者：
Koehnke, Jesko;Bent, Andrew;Houssen, Wael E.;Zollman, David;Morawitz, Falk;Shirran, Sally;Vendome, Jeremie;Nneoyiegbe, Ada F.;Trembleau, Laurent;Botting, Catherine H.;Smith, Margaret C. M.;Jaspars, Marcel;Naismith, James H.
通讯作者：
Naismith, James H.
DOI：
10.1073/pnas.1620499114
发表时间：
2017-06-20
影响因子：
11.1
作者：
Chekan, Jonathan R.;Estrada, Paola;Nair, Satish K.
通讯作者：
Nair, Satish K.
影响因子：
3.6
作者：
Agarkov, A;Greenfield, SJ;Gilbertson, SR
通讯作者：
Gilbertson, SR