Rh(II)-Catalyzed C-H Alkylation of Benzylamines with Unactivated Alkenes: The Influence of Acid on Linear and Branch Selectivity

被引：11

作者：

Das, Amrita ^{[1
]}

Chatani, Naoto ^{[1
]}

机构：

[1] Osaka Univ, Fac Engn, Dept Appl Chem, Suita, Osaka 5650871, Japan

来源：

ORGANIC LETTERS | 2021年 / 23卷 / 11期

关键词：

AROMATIC AMIDES; CATALYZED ALKYLATION; BONDS; DERIVATIVES;

D O I：

10.1021/acs.orglett.1c01224

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The Rh-catalyzed C-H alkylation of benzylamine derivatives with unactivated 1-alkenes that proceeds via a picolinamide directing group is reported. The crucial role of an acid additive in this transformation is confirmed. Aromatic acids showed high linear selectivity, and aliphatic acids provided branched alkylation products as the major product. The reaction has a broad scope for benzylamines and alkenes. Deuterium labeling experiments suggest that a Rh-carbene intermediate is involved in the case of linear product formation. A different reaction pathway, however, appears to be involved in the case of branched alkylation products, and this pathway also appeared to be a minor pathway in linear-selective reactions.

引用

页码：4273 / 4278

页数：6

共 47 条

[1]

Ackermann L., ANGEW CHEM INT EDIT, V2021, DOI 10.1002/

[2] Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope [J].

Ackermann, Lutz .

CHEMICAL REVIEWS, 2011, 111 (03) :1315-1345

[3] Unactivated Alkyl Halides in Transition-Metal-Catalyzed C-H Bond Alkylation [J].

Ankade, Shidheshwar B. ;

Shabade, Anand B. ;

Soni, Vineeta ;

Punji, Benudhar .

ACS CATALYSIS, 2021, 11 (06) :3268-3292

[4]

Arockiam PB, 2012, CHEM REV, V112, P5879, DOI [10.1021/cr300153J, 10.1021/cr300153j]

[5] A bis(thiophosphinoyl)methylene ruthenium carbene complex:: Synthesis, X-ray crystal structure, and DFT calculations of its thermally promoted reverse α-hydride migration process [J].

Cantat, T ;

Demange, M ;

Mézailles, N ;

Ricard, L ;

Jean, Y ;

Le Floch, P .

ORGANOMETALLICS, 2005, 24 (20) :4838-4841

[6] The Use of a Rhodium Catalyst/8-Aminoquinoline Directing Group in the C-H Alkylation of Aromatic Amides with Alkenes: Possible Generation of a Carbene Intermediate from an Alkene [J].

Chatani, Naoto .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2018, 91 (02) :211-222

[7] Branch-Selective Alkene Hydroarylation by Cooperative Destabilization: Iridium-Catalyzed ortho-Alkylation of Acetanilides [J].

Crisenza, Giacomo E. M. ;

Sokolova, Olga O. ;

Bower, John F. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (49) :14866-14870

[8] Branch Selective Mural-type Alkene Hydroarylation Reactions [J].

Crisenza, Giacomo E. M. ;

Bower, John F. .

CHEMISTRY LETTERS, 2016, 45 (01) :2-9

[9] Branch-Selective, Iridium-Catalyzed Hydroarylation of Monosubstituted Alkenes via a Cooperative Destabilization Strategy [J].

Crisenza, Giacomo E. M. ;

McCreanor, Niall G. ;

Bower, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (29) :10258-10261

[10] Rh(i)- and Rh(ii)-catalyzed C-H alkylation of benzylamines with alkenes and its application in flow chemistry [J].

Das, Amrita ;

Chatani, Naoto .

CHEMICAL SCIENCE, 2021, 12 (09) :3202-3209

← 1 2 3 4 5 →