Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines

	Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines
	Shi Lei 1,2; Ji Yue 1; Huang Wenxue 1; Zhou Yonggui 1
刊名	acta chimica sinica
	2014-07-15
卷号	72 期号:7 页码:820-824
关键词	chiral phosphoric acid chiral anion metathesis transfer hydrogenation isoquinolines
通讯作者	时磊 ; 周永贵
英文摘要	asymmetric hydrogenation of n-hetero aromatics offers a very straightforward and efficient method to obtain the corresponding chiral n-hetero cyclic saturated or partially saturated compounds. as one of the most challenging substrates, asymmetric hydrogenation of isoquinolines has met with limited success probably because of lower reactivity and the catalyst deactivation resulted from strong coordination. considering the prevalence of the chiral 1,2,3,4-tetrahydroisoquinoline motif in natural alkaloids and drug molecules, the development of new catalyst system for asymmetric hydrogenation of isoquinolines is highly desirable and significant. herein, a novel chiral anion metathesis strategy successfully applied for asymmetric transfer hydrogenation of isoquinolines is reported. n-protected 1-substituted 1,2-dihydroisoquinolines were obtained with high yield and up to 79% ee in the presence of hantzsch ester and chloroformate using chiral phosphoric acid as catalyst. the phosphate salt and the activated n-acyl isoquinolinium chloride undergo anion metathesis to form chiral contact ion pair, which leads to a highly enantioselective transfer hydrogenation of isoquinolines. after systematically investigating the effects of activating reagent, solvent, base, hydride donor and catalyst on this transfer hydrogenation reaction, the best result was achieved under the optimized condition as follows: 5 mol% h8-binol-derived chiral phosphoric acid as catalyst, 1.2 equivalent 2,2,2-trichloroethyl chloroformate as activator, 1.5 equivalent dimethyl 2,6-diethyl-1,4-dihydropyridine-3,5-dicarboxylate as hydride donor, 1.5 equivalent sodium carbonate as base and cyclohexane as solvent. the reaction is tolerant toward a broad range of aryl or alkyl 1-substituted isoquinoline substrates. this methodology represents one of the rare examples of asymmetric hydrogenation of this challenging substrate. the utilizing of chiral anion metathesis strategy could enable chiral phosphoric acid to catalyze more asymmetric transformation process and further researching is ongoing in our laboratory.
学科主题	物理化学
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, multidisciplinary
研究领域[WOS]	chemistry
关键词[WOS]	iridium-catalyzed hydrogenation ; friedel-crafts reaction ; diels-alder reaction ; phase-transfer catalysis ; alpha-imino esters ; bronsted acid ; heteroaromatic-compounds ; phosphoric-acid ; enantioselective reduction ; binary-acid
收录类别	SCI
语种	英语
WOS记录号	WOS:000340842000008
公开日期	2016-05-09
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/144105]
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
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China 2.Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China
推荐引用方式 GB/T 7714	Shi Lei,Ji Yue,Huang Wenxue,et al. Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines[J]. acta chimica sinica,2014,72(7):820-824.
APA	Shi Lei,Ji Yue,Huang Wenxue,&Zhou Yonggui.(2014).Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines.acta chimica sinica,72(7),820-824.
MLA	Shi Lei,et al."Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines".acta chimica sinica 72.7(2014):820-824.