trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution

被引：42

作者：

Cotman, Andrei Emanuel ^{[1
,2
,3
]}

Lozinsek, Matic ^{[2
,4
]}

Wang, Baifan ^{[1
,5
]}

Stephan, Michel ^{[1
,6
]}

Mohar, Barbara ^{[1
,6
]}

机构：

[1] Natl Inst Chem, Hajdrihova 19, SI-1000 Ljubljana, Slovenia

[2] Univ Ljubljana, Fac Chem & Chem Technol, Vecna Pot 113, SI-1000 Ljubljana, Slovenia

[3] Univ Ljubljana, Fac Pharm, Askerceva 7, Ljubljana 1000, Slovenia

[4] Jozef Stefan Inst, Dept Inorgan Chem & Technol, Jamova Cesta 39, Ljubljana 1000, Slovenia

[5] Rutgers State Univ, Dept Chem & Chem Biol, Piscataway, NJ 08854 USA

[6] PhosPhoenix SARL, 115 Rue Abbe Groult, F-75015 Paris, France

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 10期

关键词：

ENANTIOSELECTIVE TRANSFER HYDROGENATION; CATALYSTS; ALCOHOLS; LIGANDS;

D O I：

10.1021/acs.orglett.9b01069

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR-ATH) of alpha,beta-dehydro-alpha-acetamido and alpha-acetamido benzocyclic ketones to ent-trans-beta-amido alcohols is disclosed employing a new ansa-Ru(II) complex of an enantiomerically pure syn-N,N-ligand, i.e. ent-syn-ULTAM(CH2)(3)Ph. DFT calculations of the transition state structures revealed an atypical two-pronged substrate attractive stabilization engaging the commonly encountered CH/pi electrostatic interaction and a new additional O=S=O center dot center dot center dot HNAc H-bond hence favoring the trans-configured products.

引用

页码：3644 / 3648

页数：5

共 38 条

[1]

Blacker J., 2010, Green Chem. Pharm. Ind, P269, DOI [10.1002/9783527629688.ch13, DOI 10.1002/9783527629688.CH13]

[2]

Cotman A. E., 2018, THESIS

[3] Stereoarrayed 2,3-Disubstituted 1-Indanols via Ruthenium(II)-Catalyzed Dynamic Kinetic Resolution-Asymmetric Transfer Hydrogenation [J].

Cotman, Andrei Emanuel ;

Modec, Barbara ;

Mohar, Barbara .

ORGANIC LETTERS, 2018, 20 (10) :2921-2924

[4] Stereoarrayed CF3-Substituted 1,3-Diols by Dynamic Kinetic Resolution: Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation [J].

Cotman, Andrej Emanuel ;

Cahard, Dominique ;

Mohar, Barbara .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (17) :5294-5298

[5] Dynamic kinetic resolution of β-keto sulfones via asymmetric transfer hydrogenation [J].

Ding, Zhenhua ;

Yang, Jin ;

Wang, Ting ;

Shen, Zongxuan ;

Zhang, Yawen .

CHEMICAL COMMUNICATIONS, 2009, (05) :571-573

[6] Recent Developments in Asymmetric Hydrogenation and Transfer Hydrogenation of Ketones and Imines through Dynamic Kinetic Resolution [J].

Echeverria, Pierre-Georges ;

Ayad, Tahar ;

Phansavath, Phannarath ;

Ratovelomanana-Vidal, Virginie .

SYNTHESIS-STUTTGART, 2016, 48 (16) :2523-2539

[7] Asymmetric Transfer Hydrogenation of Functionalized Acetylenic Ketones [J].

Fang, Zhijia ;

Wills, Martin .

JOURNAL OF ORGANIC CHEMISTRY, 2013, 78 (17) :8594-8605

[8] Highly enantioselective synthesis of β-hydroxysulfonamides by asymmetric transfer hydrogenation [J].

Geng, Zhicong ;

Wu, Yun ;

Miao, Shifeng ;

Shen, Zongxuan ;

Zhang, Yawen .

TETRAHEDRON LETTERS, 2011, 52 (08) :907-909

[9] Rh-Catalyzed One-Pot Sequential Asymmetric Hydrogenation of α-Dehydroamino Ketones for the Synthesis of Chiral Cyclic trans-β-Amino Alcohols [J].

Hu, Qiupeng ;

Chen, Jianzhong ;

Zhang, Zhenfeng ;

Liu, Yangang ;

Zhang, Wanbin .

ORGANIC LETTERS, 2016, 18 (06) :1290-1293

[10] Racemisation in asymmetric synthesis.: Dynamic kinetic resolution and related processes in enzyme and metal catalysis [J].

Huerta, FF ;

Minidis, ABE ;

Bäckvall, JE .

CHEMICAL SOCIETY REVIEWS, 2001, 30 (06) :321-331

← 1 2 3 4 →