Enantiospecific Synthesis of α-Tertiary Amines: Ruthenium-Catalyzed Allylic Amination with Aqueous Ammonia

被引：0

作者：

Papidocha, Sven M. ^{[1
]}

Wilke, Henrik R. ^{[1
]}

Patej, Kacper J. ^{[1
]}

Isomura, Mayuko ^{[1
]}

Stucky, Tim J. ^{[1
]}

Rothenbuhler, Lukas ^{[1
]}

Carreira, Erick M. ^{[1
]}

机构：

[1] Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Lab Organ Chem, CH-8093 Zurich, Switzerland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2025年 / 147卷 / 14期

关键词：

ASYMMETRIC-SYNTHESIS; ENANTIOSELECTIVE SYNTHESIS; N-ALLYLINDOLES; CHIRAL AMINES; SUBSTITUTION; PALLADIUM; ALLYLATION; ALKYLATION; ALCOHOLS; ACID;

D O I：

10.1021/jacs.5c01928

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Ammonia stands out as the most available, cost-effective, and atom-economical source of nitrogen for organic synthesis. In the laboratory, it is safely and most conveniently handled in aqueous solution. Despite the advantages, the direct application of aqueous ammonia in the field of transition-metal catalysis remains a significant challenge. In this study, we report the first ruthenium-catalyzed allylic substitution using ammonia. The catalytic system, consisting of [Cp*Ru(MeCN)3]PF6 and a phenoxythiazoline ligand, enables the enantiospecific amination of tertiary allylic carbonates in aqueous media and affords enantioenriched primary amines as single regioisomers in high yields.

引用

页码：11675 / 11681

页数：7

共 98 条

[1] OVERALL ENANTIOSELECTIVE ALPHA-ALKYLATION OF ASPARTIC AND GLUTAMIC-ACID THROUGH DILITHIUM ENOLATOCARBOXYLATES OF 2-[3-BENZOYL-2-(TERT-BUTYL)-1-METHYL-5-OXOIMIDAZOLIDIN-4-YL]ACETIC AND 3-[3-BENZOYL-2-(TERT-BUTYL)-1-METHYL-5-OXOIMIDAZOLIDIN-4-YL]PROPIONIC ACID, RESPECTIVELY [J].

AEBI, JD ;

SEEBACH, D .

HELVETICA CHIMICA ACTA, 1985, 68 (06) :1507-1518

[2] Catalytic asymmetric rearrangement of allylic trichloroacetimidates. A practical method for preparing allylic amines and congeners of high enantiomeric purity [J].

Anderson, CE ;

Overman, LE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (41) :12412-12413

[3]

[Anonymous], 2025, PRICE LINALOOL WAS R

[4] Scope and Mechanistic Probe into Asymmetric Synthesis of α-Trisubstituted-α-Tertiary Amines by Rhodium Catalysis [J].

Arachchi, Madhawee K. ;

Schaugaard, Richard N. ;

Schlegel, H. Bernhard ;

Nguyen, Hien M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2023, 145 (36) :19642-19654

[5] Rhodium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Racemic Tertiary Allylic Trichloroacetimidates with Anilines [J].

Arnold, Jeffrey S. ;

Nguyen, Hien M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (20) :8380-8383

[6] Solvent applications of 2-methyltetrahydrofuran in organometallic and biphasic reactions [J].

Aycock, David F. .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2007, 11 (01) :156-159

[7] Cooperative Catalysis by Palladium and a Chiral Phosphoric Acid: Enantioselective Amination of Racemic Allylic Alcohols [J].

Banerjee, Debasis ;

Junge, Kathrin ;

Beller, Matthias .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (48) :13049-13053

[8] Unconventional Ethereal Solvents in Organic Chemistry: A Perspective on Applications of 2-Methyltetrahydrofuran, Cyclopentyl Methyl Ether, and 4-Methyltetrahydropyran [J].

Bijoy, Rachel ;

Agarwala, Pratibha ;

Roy, Lisa ;

Thorat, Bhaskar N. .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2022, 26 (03) :480-492

[9] Nucleophilicities of primary and secondary amines in water [J].

Brotzel, Frank ;

Chu, Ying Cheung ;

Mayr, Herbert .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (10) :3679-3688

[10] Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles [J].

Bruneau, Christian ;

Renaud, Jean-Luc ;

Demerseman, Bernard .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (20) :5178-5187

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