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

[21] Further structurally constrained analogues of cis-(6-benzhydrylpiperidin-3-yl)benzylamine with elucidation of bioactive conformation:: Discovery of 1,4-diazabicyclo[3.3.1]nonane derivatives and evaluation of their biological properties for the monoamine transporters [J].

Kolhatkar, R ;

Cook, CD ;

Ghorai, SK ;

Deschamps, J ;

Beardsley, PM ;

Reith, MEA ;

Dutta, AK .

JOURNAL OF MEDICINAL CHEMISTRY, 2004, 47 (21) :5101-5113

[22] Rhenium-Catalyzed Regioselective Alkylation of Phenols [J].

Kuninobu, Yoichiro ;

Matsuki, Takashi ;

Takai, Kazuhiko .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (29) :9914-+

[23] Design, Synthesis, and Biological Activity of Novel Triazole Sulfonamide Derivatives Containing a Benzylamine Moiety [J].

Li, Yitao ;

Yao, Wenqiang ;

Lin, Jian ;

Li, Falin ;

Wu, Yang ;

Xu, Junxing .

JOURNAL OF HETEROCYCLIC CHEMISTRY, 2019, 56 (08) :2170-2178

[24] Theoretical study of the oxidative addition of ammonia to various unsaturated low-valent transition metal species [J].

Macgregor, SA .

ORGANOMETALLICS, 2001, 20 (09) :1860-1874

[25] Comparative study on the antioxidant and biological activities of carvacrol, thymol, and eugenol derivatives [J].

Mastelic, Josip ;

Jerkovic, Igor ;

Blazevic, Ivica ;

Poljak-Blazi, Marija ;

Borovic, Suzana ;

Ivancic-Bace, Ivana ;

Smrecki, Vilko ;

Zarkovic, Neven ;

Brcic-Kostic, Krunoslav ;

Vikic-Topic, Drazen ;

Mueller, Norbert .

JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, 2008, 56 (11) :3989-3996

[26] Direct Access to Parent Amido Complexes of Rhodium and Iridium through N?H Activation of Ammonia [J].

Mena, Inmaculada ;

Casado, Miguel A. ;

Garcia-Orduna, Pilar ;

Polo, Victor ;

Lahoz, Fernando J. ;

Fazal, Atif ;

Oro, Luis A. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (49) :11735-11738

[27] Preparation and Antiviral Activity of Some New C3- and Cs-Symmetrical Tri-Substituted Triazine Derivatives Having Benzylamine Substituents [J].

Mibu, Nobuko ;

Yokomizo, Kazumi ;

Sano, Marina ;

Kawaguchi, Yuuna ;

Morimoto, Kenta ;

Shimomura, Syunsuke ;

Sato, Ryo ;

Hiraga, Nozomi ;

Matsunaga, Aya ;

Zhou, Jian-Rong ;

Ohata, Tomonori ;

Aki, Hatsumi ;

Sumoto, Kunihiro .

CHEMICAL & PHARMACEUTICAL BULLETIN, 2018, 66 (08) :830-838

[28] EFFICIENT CATALYTIC ADDITION OF AROMATIC CARBON-HYDROGEN BONDS TO OLEFINS [J].

MURAI, S ;

KAKIUCHI, F ;

SEKINE, S ;

TANAKA, Y ;

KAMATANI, A ;

SONODA, M ;

CHATANI, N .

NATURE, 1993, 366 (6455) :529-531

[29] The reductive cleavage of picolinic amides [J].

O'Donovan, Daniel H. ;

De Fusco, Claudia ;

Spring, David R. .

TETRAHEDRON LETTERS, 2016, 57 (27-28) :2962-2964

[30] Rh(I)-catalyzed Addition of the ortho C-H Bond in Aryl Sulfonamides to Maleimides [J].

Ohara, Nozomi ;

Rej, Supriya ;

Chatani, Naoto .

CHEMISTRY LETTERS, 2020, 49 (09) :1053-1057

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