Iridium-catalyzed asymmetric trans-selective hydrogenation of 1,3-disubstituted isoquinolines

被引：12

作者：

Kim, Alexia N. ^{[1
]}

Ngamnithiporn, Aurapat ^{[1
,2
]}

Bartberger, Michael D. ^{[3
]}

Stoltz, Brian M. ^{[1
]}

机构：

[1] CALTECH, Warren & Katharine Schlinger Lab Chem & Chem Engn, Div Chem & Chem Engn, Pasadena, CA 91125 USA

[2] Chulabhorn Res Inst, Lab Med Chem, 54 Kamphaeng Phet 6 Rd, Bangkok 10210, Thailand

[3] 1200 Pharma LLC, 844 East Green St,Suite 204, Pasadena, CA 91101 USA

来源：

CHEMICAL SCIENCE | 2022年 / 13卷 / 11期

关键词：

BETA-HYDRIDE ELIMINATION; ENANTIOSELECTIVE HYDROGENATION; ARENE HYDROGENATION; COMPLEXES; EFFICIENT; RUTHENIUM;

D O I：

10.1039/d1sc06729j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The development of the first asymmetric trans-selective hydrogenation of 1,3-disubstituted isoquinolines is reported. Utilizing [Ir(cod)Cl](2) and a commercially available chiral Josiphos ligand, a variety of differentially substituted isoquinolines are hydrogenated to produce enantioenriched trans-tetrahydroisoquinolines in good yield with high levels of enantioselectivity. Directing group studies demonstrate that the hydroxymethyl functionality at the C1 position is critical for hydrogenation to favor the trans-diastereomer. Preliminary mechanistic studies reveal that non-coordinating chlorinated solvents and halide additives are crucial to enable trans-selectivity.

引用

页码：3227 / 3232

页数：6

共 39 条

[1] Metal-Catalyzed Asymmetric Hydrogenation of C=N Bonds [J].

Abdine, Racha Abed Ali ;

Hedouin, Gaspard ;

Colobert, Francoise ;

Wencel-Delord, Joanna .

ACS CATALYSIS, 2021, 11 (01) :215-247

[2] A diversity of recently reported methodology for asymmetric imine reduction [J].

Barrios-Rivera, Jonathan ;

Xu, Yingjian ;

Wills, Martin ;

Vyas, Vijyesh K. .

ORGANIC CHEMISTRY FRONTIERS, 2020, 7 (20) :3312-3342

[3] Recent Progress and Applications of Transition-Metal-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of Ketones and Imines through Dynamic Kinetic Resolution [J].

Betancourt, Ricardo Molina ;

Echeverria, Pierre-Georges ;

Ayad, Tahar ;

Phansavath, Phannarath ;

Ratovelomanana-Vidal, Virginie .

SYNTHESIS-STUTTGART, 2021, 53 (01) :30-50

[4] MECHANISM OF A DIRECTLY OBSERVED BETA-HYDRIDE ELIMINATION PROCESS OF IRIDIUM ALKOXO COMPLEXES [J].

BLUM, O ;

MILSTEIN, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (16) :4582-4594

[5] Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation [J].

Cabre, Albert ;

Verdaguer, Xavier ;

Riera, Antoni .

CHEMICAL REVIEWS, 2022, 122 (01) :269-339

[6] Asymmetric Hydrogenation of Isoquinolines and Pyridines Using Hydrogen Halide Generated in Situ as Activator [J].

Chen, Mu-Wang ;

Ji, Yue ;

Wang, Jie ;

Chen, Qing-An ;

Shi, Lei ;

Zhou, Yong-Gui .

ORGANIC LETTERS, 2017, 19 (18) :4988-4991

[7] Coordinating ability of anions and solvents towards transition metals and lanthanides [J].

Diaz-Torres, Raul ;

Alvarez, Santiago .

DALTON TRANSACTIONS, 2011, 40 (40) :10742-10750

[8] Chiral iridium xyliphos complexes for the catalytic imine hydrogenation leading to the metolachlor herbicide:: Isolation of catalyst-substrate adducts [J].

Dorta, R ;

Broggini, D ;

Stoop, R ;

Rüegger, H ;

Spindler, F ;

Togni, A .

CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (01) :267-278

[9]

Fagnou K, 2002, ANGEW CHEM INT EDIT, V41, P26, DOI 10.1002/1521-3773(20020104)41:1<26::AID-ANIE26>3.0.CO

[10]

2-9

← 1 2 3 4 →