气候变化领域集成服务门户(CCPortal): Asymmetric nucleophilic fluorination under hydrogen bonding phase-transfer catalysis

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DOI	10.1126/science.aar7941
	Asymmetric nucleophilic fluorination under hydrogen bonding phase-transfer catalysis
	Pupo G.; Ibba F.; Ascough D.M.H.; Vicini A.C.; Ricci P.; Christensen K.E.; Pfeifer L.; Morphy J.R.; Brown J.M.; Paton R.S.; Gouverneur V.
发表日期	2018
ISSN	0036-8075
起始页码	638
结束页码	642
卷号	360 期号:6389
英文摘要	Common anionic nucleophiles such as those derived from inorganic salts have not been used for enantioselective catalysis because of their insolubility. Here, we report that merging hydrogen bonding and phase-transfer catalysis provides an effective mode of activation for nucleophiles that are insoluble in organic solvents. This catalytic manifold relies on hydrogen bonding complexation to render nucleophiles soluble and reactive, while simultaneously inducing asymmetry in the ensuing transformation. We demonstrate the concept using a chiral bis-urea catalyst to form a tridentate hydrogen bonding complex with fluoride from its cesium salt, thereby enabling highly efficient enantioselective ring opening of episulfonium ion. This fluorination method is synthetically valuable considering the scarcity of alternative protocols and points the way to wider application of the catalytic approach with diverse anionic nucleophiles. 2017 © The Authors
英文关键词	cesium salt; episulfonium ion; fluoride; organic solvent; sulfonium derivative; unclassified drug; activation energy; catalysis; catalyst; cesium; chemical bonding; complexation; complexity; hydrogen; inorganic salt; solvent; transformation; Article; asymmetric catalysis; biotransformation; catalyst; chirality; complex formation; desymmetrization; electron; enantioselectivity; enzyme mechanism; fluorination; hydrogen bond; mathematical analysis; molecular dynamics; nucleophilicity; phase transfer catalysis; priority journal
语种	英语
来源期刊	Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/245143
作者单位	University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, United Kingdom; Medicinal Chemistry, Eli Lilly and Company Limited, Erl Wood Manor, Sunninghill Road, Windlesham, GU20 6PH, United Kingdom
推荐引用方式 GB/T 7714	Pupo G.,Ibba F.,Ascough D.M.H.,et al. Asymmetric nucleophilic fluorination under hydrogen bonding phase-transfer catalysis[J],2018,360(6389).
APA	Pupo G..,Ibba F..,Ascough D.M.H..,Vicini A.C..,Ricci P..,...&Gouverneur V..(2018).Asymmetric nucleophilic fluorination under hydrogen bonding phase-transfer catalysis.Science,360(6389).
MLA	Pupo G.,et al."Asymmetric nucleophilic fluorination under hydrogen bonding phase-transfer catalysis".Science 360.6389(2018).