亲爱的研友该休息了!由于当前在线用户较少,发布求助请尽量完整的填写文献信息,科研通机器人24小时在线,伴您度过漫漫科研夜!身体可是革命的本钱,早点休息,好梦!

Properties of Configurationally Stable Atropoenantiomers in Macrocyclic Natural Products and the Chrysophaentin Family

阿托品 立体中心 手性(物理) 轴手性 化学 构象异构 高分子 立体化学 立体异构 分子 对映选择合成 有机化学 物理 手征对称破缺 生物化学 量子力学 催化作用 Nambu–Jona Lasinio模型 夸克
作者
Carole A. Bewley,Gary A. Sulikowski,Zhongyue Yang,Giuseppe Bifulco,Hyo-Moon Cho,Christopher R. Fullenkamp
出处
期刊:Accounts of Chemical Research [American Chemical Society]
卷期号:56 (4): 414-424 被引量:1
标识
DOI:10.1021/acs.accounts.2c00648
摘要

development of antibiotics, antineoplastics, and therapeutics for other diseases. Natural products are unique among all other small molecules in that they are produced by dedicated enzymatic assembly lines that are the protein products of biosynthetic gene clusters. As the products of chiral macromolecules, natural products have distinct three-dimensional shapes and stereochemistry is often encoded in their structures through the presence of stereocenters, or in the case of molecules that lack a stereocenter, the presence of an axis or plane of chirality. In the latter forms of chirality, if the barrier to rotation about the chiral axis or chiral plane is sufficiently high, stable conformers may exist allowing for isolation of discrete conformers, also known as atropisomers. Importantly, the diverse functions and biological activities of natural products are contingent upon their structures, stereochemistry and molecular shape. With continued innovation in methods for natural products discovery, synthetic chemistry, and analytical and computational tools, new insights into atropisomerism in natural products and related scaffolds are being made. As molecular complexity increases, more than one form of stereoisomerism may exist in a single compound (for example, point chirality, chiral axes, and chiral planes), sometimes creating atypical or noncanonical atropisomers, a term used to distinguish physically noninterconvertable atropisomers from typical atropisomers.Here we provide an account of the discovery and unusual structural and stereochemical features of the chrysophaentins, algal derived inhibitors of the bacterial cytoskeletal protein FtsZ and its associated protein partners. Eleven members of the chrysophaentin family have been discovered to date; seven of these are macrocyclic bis-bibenzyl ethers wherein the site of the ether linkage yields either a symmetrical or asymmetrical macrocyclic ring system. The asymmetrical ring system is highly strained and corresponds to the compounds having the most potent antimicrobial activity among the family. We review the structure elucidation and NMR properties that indicate restricted rotation between axes of two biaryl ethers, and the plane represented by the substituted 2-Z-butene bridge common to all of the macrocycles. Computational studies that corroborate high barriers to rotation about one representative plane, on the order of 20+ kcal/mol are presented. These barriers to rotation fix the conformation of the macrocycle into a bowl-like structure and suggest that an atropisomer should exist. Experimental evidence for atropisomerism is presented, consistent with computational predictions. These properties are discussed in the context of the total synthesis of 9-dechlorochrysophaenin A and its ring C isomers. Last, we discuss the implications for the presence of enantiomers in the biological activity and macrocyclization of the natural product.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
大幅提高文件上传限制,最高150M (2024-4-1)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
10秒前
14秒前
19秒前
柠檬发布了新的文献求助10
23秒前
眯眯眼的南琴完成签到,获得积分10
26秒前
27秒前
27秒前
鲨鱼辣椒完成签到,获得积分10
37秒前
demo完成签到,获得积分10
38秒前
39秒前
领会完成签到 ,获得积分10
40秒前
鲨鱼辣椒发布了新的文献求助10
41秒前
leilei完成签到,获得积分10
45秒前
45秒前
蛋邑完成签到,获得积分10
51秒前
55秒前
思源应助Langsam采纳,获得50
1分钟前
he完成签到 ,获得积分10
1分钟前
负责念蕾完成签到 ,获得积分10
1分钟前
上官凯凯完成签到 ,获得积分10
1分钟前
科研通AI2S应助科研通管家采纳,获得10
1分钟前
123应助科研通管家采纳,获得10
1分钟前
科研通AI2S应助科研通管家采纳,获得10
1分钟前
NexusExplorer应助科研通管家采纳,获得10
1分钟前
FashionBoy应助科研通管家采纳,获得10
1分钟前
JamesPei应助科研通管家采纳,获得10
1分钟前
怀玉完成签到 ,获得积分10
1分钟前
1分钟前
李昕123完成签到 ,获得积分10
1分钟前
1分钟前
1分钟前
小小aa16完成签到,获得积分10
2分钟前
科研通AI2S应助别踩痛了雪采纳,获得10
2分钟前
Langsam发布了新的文献求助50
2分钟前
aaa发布了新的文献求助10
2分钟前
2分钟前
2分钟前
敉_发布了新的文献求助10
2分钟前
2分钟前
狐狸萌萌哒完成签到 ,获得积分10
2分钟前
高分求助中
좌파는 어떻게 좌파가 됐나:한국 급진노동운동의 형성과 궤적 2500
Sustainability in Tides Chemistry 1500
TM 5-855-1(Fundamentals of protective design for conventional weapons) 1000
Cognitive linguistics critical concepts in linguistics 800
Threaded Harmony: A Sustainable Approach to Fashion 799
Livre et militantisme : La Cité éditeur 1958-1967 500
氟盐冷却高温堆非能动余热排出性能及安全分析研究 500
热门求助领域 (近24小时)
化学 医学 生物 材料科学 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 基因 遗传学 催化作用 物理化学 免疫学 量子力学 细胞生物学
热门帖子
关注 科研通微信公众号,转发送积分 3052387
求助须知:如何正确求助?哪些是违规求助? 2709716
关于积分的说明 7418100
捐赠科研通 2354190
什么是DOI,文献DOI怎么找? 1245828
科研通“疑难数据库(出版商)”最低求助积分说明 605892
版权声明 595899