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学科主题: 物理化学
题名: Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines
作者: Shi Lei1, 2;  Ji Yue1;  Huang Wenxue1;  Zhou Yonggui1
通讯作者: 时磊 ;  周永贵
关键词: chiral phosphoric acid ;  chiral anion metathesis ;  transfer hydrogenation ;  isoquinolines
刊名: ACTA CHIMICA SINICA
发表日期: 2014-07-15
DOI: 10.6023/A14050391
卷: 72, 期:7, 页:820-824
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary
研究领域[WOS]: Chemistry
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.
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
语种: 英语
WOS记录号: WOS:000340842000008
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/144105
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
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.
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