DICP OpenIR
Subject Area物理化学
Application of Chiral Anion Metathesis Strategy in Asymmetric Transfer Hydrogenation of Isoquinolines
Shi Lei1,2; Ji Yue1; Huang Wenxue1; Zhou Yonggui1; Shi L(时磊); Zhou YG(周永贵)
KeywordChiral Phosphoric Acid Chiral Anion Metathesis Transfer Hydrogenation Isoquinolines
Source PublicationACTA CHIMICA SINICA
2014-07-15
DOI10.6023/A14050391
Volume72Issue:7Pages:820-824
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Multidisciplinary
WOS Research AreaChemistry
WOS KeywordIRIDIUM-CATALYZED HYDROGENATION ; FRIEDEL-CRAFTS REACTION ; DIELS-ALDER REACTION ; PHASE-TRANSFER CATALYSIS ; ALPHA-IMINO ESTERS ; BRONSTED ACID ; HETEROAROMATIC-COMPOUNDS ; PHOSPHORIC-ACID ; ENANTIOSELECTIVE REDUCTION ; BINARY-ACID
AbstractAsymmetric 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.
Language英语
WOS IDWOS:000340842000008
Citation statistics
Cited Times:8[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/144105
Collection中国科学院大连化学物理研究所
Corresponding AuthorShi L(时磊); Zhou YG(周永贵)
Affiliation1.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
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,时磊,&周永贵.(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.
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