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Deciphering the Origin and Formation of aminopyrrole Moiety in Kosinostatin Biosynthesis

Chinese Journal of Chemistry 2021年第12期39卷 3329-3333页

作者： Yu Hu Qiang Zhou Zhuan Zhang Hai-Xue Pan Yulia Ilina Mikko Metsa-Ketela Yasuhiro Igarashi Gong-Li Tang State Key Laboratory of Bio-organic and Natural Products Chemistry Center for Excellence in Molecular SynthesisShanghai Institute of Organic ChemistryUniversity of Chinese Academy of Sciences(CAS)CASShanghai 200032China The Research Center of Chiral Drugs Innovation Research Institute of Traditional Chinese MedicineShanghai University of Traditional Chinese MedicineShanghai 201203China School of Chemistry and Materials Science Hangzhou Institute for Advanced StudyUniversity of Chinese Academy of Sciences1 Sub-lane XiangshanHangzhouZhejiang 310024China Department of Biochemistry University of TurkuVatselankatu 2FIN-20014Finland Biotechnology Research Center Toyama Prefectural University 5180 KurokawaImizuToyama 939-0398Japan

Kosinostatin(KST)contains an uncommon aminopyrrole moiety,whose biosynthesis has remained elusive.Herein,aminopyrrolinic acid,which was generated by an L-ectoine synthase-like enzyme KstB3 via cyclization of L-glutamine,was identified to be the real substrate of adenylation enzyme KstB1.Subsequently,a FAD-dependent dehydrogenase KstB4 along with a transglutaminase-like enzyme KstB6 were also involved in formation of aminopyrrole.These results provided an unusual pathway for 2-aminopyrrole formation in KST biosynthesis.

关键词： Biosynthesis aminopyrrole Kosihbstatin Cyclization Hydrolysis

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Synthesis and structural diversity of alkali-metal(Li,Na,K) alkyl magnesiates containing bidentate aminopyrrolyl ligand

Synthesis and structural diversity of alkali-metal(Li,Na,K) ...

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中国化学会第八届全国配位化学会议

作者： Zhiqiang Guo Xiaoqin Wu Xuehong Wei Scientific Instrument Center Shanxi University School of Chemistry and Chemical Engineering Shanxi University

The advantages of bimetallic "ate" complexes have over conventional alkali metal reagents(use of milder reaction conditions,better functional group tolerance,access to hitherto inaccessible synthetic chemistry,etc.) ensure that this area of research will blossom further in the coming years[1].Most of these studies have focused on main-group metal systems,which combine an alkalimetal with a more electronegative metal such as Mg,Zn(pseudo main group because of its s→s reactivity),or Al[2].As a part of our ongoing interest in the development of new reaction systems based on bimetallic compounds supported by multidentate pyrrole-based ligands[3],herein we have focused on the versatile bonding modes of bidentate dianionic pyrrolyl ligand[C H NH(2-CH NHBu)]as model proligand,And demonstrated three alkalimetal(Li,Na) alkyl magnesiates with a variety of intriguing structures.These new types of alkali-metal alkyl magnesiates shed a new light on pyrrolyl-based complexes and could provide useful tools in the field of bimetallic cooperativity.

关键词： Synthesis Structural diversity Alkali-metal magnesiates aminopyrrole

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