Syntheses of sceptrins and nakamuric acid and insights into the   biosyntheses of pyrrole-imidazole dimers

doi:10.1039/c5qo00165j

CORC > 北京大学 > 化学与分子工程学院

	Syntheses of sceptrins and nakamuric acid and insights into the biosyntheses of pyrrole-imidazole dimers
	Wang, Xiaolei ; Gao, Yang ; Ma, Zhiqiang ; Rodriguez, Rodrigo A. ; Yu, Zhi-Xiang ; Chen, Chuo
刊名	Organic Chemistry Frontiers
	2015
关键词	VISIBLE-LIGHT PHOTOCATALYSIS SPONGE AGELAS-CONIFERA X-RAY CRYSTALLOGRAPHY DETERMINE ABSOLUTE-CONFIGURATION PHOTOREDOX CATALYSIS DIELS-ALDER GLUTAMIC-ACID STEREOSELECTIVE-SYNTHESIS BROMOPYRROLE ALKALOIDS ASYMMETRIC-SYNTHESIS
DOI	10.1039/c5qo00165j
英文摘要	Sceptrins and nakamuric acid are structurally unique antibiotics isolated from marine sponges. Recent studies suggest that the biosynthesis of these dimeric pyrrole-imidazole alkaloids involves a single-electron transfer (SET)-promoted [2 + 2] cycloaddition to form their cyclobutane core skeletons. We describe herein the biomimetic syntheses of racemic sceptrin and nakamuric acid. We also report the asymmetric syntheses of sceptrin, bromosceptrin, and dibromosceptrin in their natural enantiomeric form. We further provide mechanistic insights into the pathway selectivity of the SET-promoted [2 + 2] and [4 + 2] cycloadditions that lead to the divergent formation of the sceptrin and ageliferin core skeletons. Both the [2 + 2] and [4 + 2] cycloadditions are stepwise reactions, with the [2 + 2] pathway kinetically and thermodynamically favored over the [4 + 2] pathway. For the [2 + 2] cycloaddition, the dimerization of pyrrole-imidazole monomers is rate-limiting, whereas for the [4 + 2] cycloaddition, the cyclization is the slowest step.; NIH [NIGMS R01-GM079554]; Welch Foundation [I-1868]; UT Southwestern; SCI(E); PubMed; ARTICLE; Chuo.Chen@UTSouthwestern.edu; 8; 978-984; 2
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/418252]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Xiaolei,Gao, Yang,Ma, Zhiqiang,et al. Syntheses of sceptrins and nakamuric acid and insights into the biosyntheses of pyrrole-imidazole dimers[J]. Organic Chemistry Frontiers,2015.
APA	Wang, Xiaolei,Gao, Yang,Ma, Zhiqiang,Rodriguez, Rodrigo A.,Yu, Zhi-Xiang,&Chen, Chuo.(2015).Syntheses of sceptrins and nakamuric acid and insights into the biosyntheses of pyrrole-imidazole dimers.Organic Chemistry Frontiers.
MLA	Wang, Xiaolei,et al."Syntheses of sceptrins and nakamuric acid and insights into the biosyntheses of pyrrole-imidazole dimers".Organic Chemistry Frontiers (2015).