Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates

被引：70

作者：

Chen, Wenyong ^{[1
]}

Chen, Ming ^{[1
]}

Hartwig, John F. ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 45期

关键词：

ASYMMETRIC ALLYLIC SUBSTITUTIONS; COMPLEXES-RESTING STATES; ALPHA-ALLYLATION; ALKYLATION REACTIONS; ALDOL REACTIONS; QUATERNARY; LITHIUM; ACIDS; CONSTRUCTION; BENZYLATION;

D O I：

10.1021/ja506500u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

引用

页码：15825 / 15828

页数：4

共 64 条

[1] Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies [J].

Behenna, Douglas C. ;

Mohr, Justin T. ;

Sherden, Nathaniel H. ;

Marinescu, Smaranda C. ;

Harned, Andrew M. ;

Tani, Kousuke ;

Seto, Masaki ;

Ma, Sandy ;

Novak, Zoltan ;

Krout, Michael R. ;

McFadden, Ryan M. ;

Roizen, Jennifer L. ;

Enquist, John A., Jr. ;

White, David E. ;

Levine, Samantha R. ;

Petrova, Krastina V. ;

Iwashita, Akihiko ;

Virgil, Scott C. ;

Stoltz, Brian M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (50) :14199-14223

[2]

Braun M, 2000, ANGEW CHEM INT EDIT, V39, P3494, DOI 10.1002/1521-3773(20001002)39:19<3494::AID-ANIE3494>3.0.CO

[3]

2-4

[4]

Braun M., 2005, SYNLETT, V2005, P2968

[5] Palladium-catalyzed diastereoselective and enantioselective allylic alkylations of ketone enolates [J].

Braun, Manfred ;

Meier, Thorsten ;

Laicher, Frank ;

Meletis, Panos ;

Fidan, Mesut .

ADVANCED SYNTHESIS & CATALYSIS, 2008, 350 (02) :303-314

[6] Palladium-Catalyzed Regio-, Diastereo-, and Enantioselective Allylic Alkylation of Acylsilanes with Monosubstituted Allyl Substrates [J].

Chen, Jian-Ping ;

Ding, Chang-Hua ;

Liu, Wei ;

Hou, Xue-Long ;

Dai, Li-Xin .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (44) :15493-15495

[7] Iridium-Catalyzed Enantioselective Allylic Substitution of Unstabilized Enolates Derived from α,β-Unsaturated Ketone [J].

Chen, Ming ;

Hartwig, John F. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (33) :8691-8695

[8] Cation Control of Diastereoselectivity in Iridium-Catalyzed Allylic Substitutions. Formation of Enantioenriched Tertiary Alcohols and Thioethers by Allylation of 5H-Oxazol-4-ones and 5H-Thiazol-4-ones [J].

Chen, Wenyong ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (01) :377-382

[9] Control of Diastereoselectivity for Iridium-Catalyzed Allylation of a Prochiral Nucleophile with a Phosphate Counterion [J].

Chen, Wenyong ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (06) :2068-2071

[10] Iridium-Catalyzed Regioselective and Enantioselective Allylation of Trimethylsiloxyfuran [J].

Chen, Wenyong ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (37) :15249-15252

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