Catalytic Tandem Markovnikov Hydroamination-Alkynylation and Markovnikov Hydroamination-Hydrovinylation

被引：16

作者：

Palchak, Zachary L. ^{[1
]}

Lussier, Daniel J. ^{[1
]}

Pierce, Conor J. ^{[1
]}

Yoo, Hoseong ^{[1
]}

Larsen, Catharine H. ^{[1
]}

机构：

[1] Univ Calif Riverside, Dept Chem, Riverside, CA 92512 USA

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2015年 / 357卷 / 2-3期

基金：

美国国家科学基金会;

关键词：

alkynes; amines; copper catalysis; green chemistry; tandem reactions; H BOND ACTIVATION; INTERMOLECULAR HYDROAMINATION; TERMINAL ALKYNES; INTERNAL ALKYNES; DIRECT ADDITION; ALKENES; AMINES; GOLD; 1,3-DIENES; COMPLEX;

D O I：

10.1002/adsc.201401037

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

A tandem hydroamination-alkynylation was developed as a unique mode of accessing tetra-substituted propargylic amines. The first equivalent of an alkyne acts as the electrophile in a Markovnikov hydroamination. The resultant ketimine intermediate is attacked by the second equivalent of alkyne in its nucleophilic copper acetylide form. Studies on the role of each component indicate that the overall reaction is first-order in copper, amine, and alkyne. In addition, a tandem hydroamination-hydrovinylation provides for an unprecedented one-step synthesis of a 1-amino-1,3-butadiene from phenylacetylene and morpholine.

引用

页码：539 / 548

页数：10

共 77 条

[1] Transition-metal-catalyzed addition of heteroatom-hydrogen bonds to alkynes [J].

Alonso, F ;

Beletskaya, IP ;

Yus, M .

CHEMICAL REVIEWS, 2004, 104 (06) :3079-3159

[2]

[Anonymous], ANGEW CHEM

[3] Palladium catalyzed alkenyl amination:: from enamines to heterocyclic synthesis [J].

Barluenga, J ;

Valdés, C .

CHEMICAL COMMUNICATIONS, 2005, (39) :4891-4901

[4] Palladium-catalyzed amination of 1-bromo- and 1-chloro-1,3-butadienes:: A general method for the synthesis of 1-amino-1,3-butadienes [J].

Barluenga, J ;

Aznar, F ;

Moriel, P ;

Valdés, C .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (13-15) :1697-1701

[5] Mild Reaction Conditions for the Terminal Deuteration of Alkynes [J].

Bew, Sean P. ;

Hiatt-Gipson, Glyn D. ;

Lovell, Jenny A. ;

Poullain, Christophe .

ORGANIC LETTERS, 2012, 14 (02) :456-459

[6] Recent Developments in Asymmetric Alkynylation of Imines [J].

Blay, G. ;

Monleon, A. ;

Pedro, J. R. .

CURRENT ORGANIC CHEMISTRY, 2009, 13 (15) :1498-1539

[7] Efficient gold-catalyzed hydroamination of 1,3-dienes [J].

Brouwer, C ;

He, C .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (11) :1744-1747

[8]

Brouwer C., 2006, ANGEW CHEM, V118, P1776

[9] Quaternary centres bearing nitrogen (α-tertiary amines) as products of molecular rearrangements [J].

Clayden, Jonathan ;

Donnard, Morgan ;

Lefranc, Julien ;

Tetlow, Daniel J. .

CHEMICAL COMMUNICATIONS, 2011, 47 (16) :4624-4639

[10] Gold-Catalyzed Carbon-Heteroatom Bond-Forming Reactions [J].

Corma, A. ;

Leyva-Perez, A. ;

Sabater, Maria J. .

CHEMICAL REVIEWS, 2011, 111 (03) :1657-1712

← 1 2 3 4 5 6 7 8 →