Modulation of Conformational Preferences of Heteroaromatic Ethers and Amides through Protonation and Ionization: Charge Effect

doi:10.1002/open.201900103

	Modulation of Conformational Preferences of Heteroaromatic Ethers and Amides through Protonation and Ionization: Charge Effect
	Dai, Wenshuai 1,2; Zhang, Zhe 1,2; Du, Yikui 1
刊名	CHEMISTRYOPEN
	2019-07-01
卷号	8 期号:7 页码:840-851
关键词	conformational modulation heteroaromatic ethers heteroaromatic amides protonation ionization
ISSN号	2191-1363
DOI	10.1002/open.201900103
通讯作者	Du, Yikui(ydu@iccas.ac.cn)
英文摘要	Multiple approaches reveal the strong effects of a positive charge introduced by protonation or ionization on the conformation of o-heteroaromatic ethers and amides. The ethers and amides containing an ortho-N heteroatom are syn-preferring while those containing an ortho-O or ortho-S heteroatom are mostly anti-preferring. However, for all the monocyclic o=heteroaromatic ethers and amides, the protonated ones are all anti-preferring while the ionized ones are all syn-preferring. Interestingly, although both the protonation and ionization introduce a positive charge, they have such different effects on molecular conformation, very informative for understanding the origin of conformational preferences. Detailed analysis shows that the population of the introduced positive charge dictates the conformational preferences via electrostatic and orbital interactions. Compared to ortho-heteroatoms, meta-heteroatoms have weaker effect on conformational preference. Achieved by complete inductive method, the regularity of conformational preferences and switching provides easy ways to modulate conformers (by pH or redox), and makes this kind of ether or amide bond a conformational hinge applicable to design of functional molecules (drugs and materials) and modulation of molecular biological processes.
资助项目	National Natural Science Foundation of China[20973180] ; National Natural Science Foundation of China[21190034]
WOS关键词	2-METHOXYPYRIDINE ; DENSITY ; ISOMERIZATION ; SIGNATURE ; DISCOVERY ; POTENT ; NMR
WOS研究方向	Chemistry
语种	英语
出版者	WILEY-V C H VERLAG GMBH
WOS记录号	WOS:000477965100005
资助机构	National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/173703]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Du, Yikui
作者单位	1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Sch Chem Engn, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Dai, Wenshuai,Zhang, Zhe,Du, Yikui. Modulation of Conformational Preferences of Heteroaromatic Ethers and Amides through Protonation and Ionization: Charge Effect[J]. CHEMISTRYOPEN,2019,8(7):840-851.
APA	Dai, Wenshuai,Zhang, Zhe,&Du, Yikui.(2019).Modulation of Conformational Preferences of Heteroaromatic Ethers and Amides through Protonation and Ionization: Charge Effect.CHEMISTRYOPEN,8(7),840-851.
MLA	Dai, Wenshuai,et al."Modulation of Conformational Preferences of Heteroaromatic Ethers and Amides through Protonation and Ionization: Charge Effect".CHEMISTRYOPEN 8.7(2019):840-851.