Facile Synthesis of Substituted 4-Alkoxy-2-oxazolines and Exploration of the Reaction Mechanism

被引：2

作者：

Zhu, Jianming ^{[1
,2
]}

Li, Xiaolong ^{[3
]}

Wang, Guimin ^{[1
,2
]}

Li, Bo ^{[1
,2
]}

Xu, Zhijian ^{[1
,2
]}

Tian, Shikai ^{[3
]}

Hall, Adrian ^{[4
]}

Shen, Jingshan ^{[1
,2
]}

Shi, Jiye ^{[4
,5
]}

Zhu, Weiliang ^{[1
,2
]}

机构：

[1] Chinese Acad Sci, CAS Key Lab Receptor Res, Shanghai 201203, Peoples R China

[2] Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, Shanghai 201203, Peoples R China

[3] Univ Sci & Technol China, Nano Sci & Technol Inst, Suzhou 215123, Peoples R China

[4] UCB Biopharma SPRL, Chemin Foriest, B-1420 Braine Lalleud, Belgium

[5] Univ Oxford, Kellogg Coll, 60-62 Banbury Rd, Oxford OX2 6PN, England

来源：

SYNTHESIS-STUTTGART | 2016年 / 48卷 / 09期

基金：

上海市自然科学基金;

关键词：

4-alkoxy-2-oxazoline; benzonitrile; beta-hydroxyacetal; trifluoromethanesulfonic acid; reaction mechanism; quantum chemistry calculation; OXAZOLES; HETEROCYCLES; AMINATION; BOND;

D O I：

10.1055/s-0035-1561386

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Substituted 4-alkoxy-2-oxazolines have been synthesized via the reaction of nitriles with beta-hydroxyacetals promoted by trifluoromethanesulfonic acid. The reaction is proposed to be initiated by the protonation of the acetals to produce carbocations that are then attacked by nitrogen atom of the nitriles, followed by an intramolecular cyclization reaction to form the 4-alkoxy-2-oxazolines. The proposed reaction mechanism has been validated by quantum chemistry calculations, key intermediate synthesis, and NMR spectra.

引用

页码：1331 / 1343

页数：13

共 28 条

[1] Anodic methoxylation and acetoxylation of imines and imidates [J].

Baba, D ;

Fuchigami, T .

TETRAHEDRON LETTERS, 2003, 44 (15) :3133-3136

[2] Copper-triggered three-component reaction of CF3CHN2, nitriles, and aldehydes: highly diastereoselective synthesis of CF3-substituted oxazolines and vicinal amino alcohols [J].

Cai, Ai-Jie ;

Zheng, Yan ;

Ma, Jun-An .

CHEMICAL COMMUNICATIONS, 2015, 51 (43) :8946-8949

[3] Nickel-Catalyzed Biaryl Coupling of Heteroarenes and Aryl Halides/Triflates [J].

Canivet, Jerome ;

Yamaguchi, Junichiro ;

Ban, Ikuya ;

Itami, Kenichiro .

ORGANIC LETTERS, 2009, 11 (08) :1733-1736

[4] Enantioselective copper-catalyzed propargylic amination [J].

Detz, Remko J. ;

Delville, Marielle M. E. ;

Hiemstra, Henk ;

van Maarseveen, Jan H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (20) :3777-3780

[5] α-Pyrones and Diketopiperazine Derivatives from the Marine-Derived Actinomycete Nocardiopsis dassonvillei HR10-5 [J].

Fu, Peng ;

Liu, Peipei ;

Qu, Haijun ;

Wang, Yi ;

Chen, Dianfeng ;

Wang, Hui ;

Li, Jing ;

Zhu, Weiming .

JOURNAL OF NATURAL PRODUCTS, 2011, 74 (10) :2219-2223

[6] I2-Catalyzed C-O Bond Formation and Dehydrogenation: Facile Synthesis of Oxazolines and Oxazoles Controlled by Bases [J].

Gao, Wen-Chao ;

Hu, Fei ;

Huo, Yu-Ming ;

Chang, Hong-Hong ;

Li, Xing ;

Wei, Wen-Long .

ORGANIC LETTERS, 2015, 17 (15) :3914-3917

[7] Stereoselective electrogeneration of (E)-4-alkoxy-2-phenyl-5-chloro-2-oxazolines by cathodic reduction of N-(1-alkoxy-2,2,2-trichloroethyl)benzamides [J].

Guirado, A ;

Andreu, R ;

Martiz, B ;

Gálvez, J .

TETRAHEDRON, 2004, 60 (04) :987-991

[8] X-RAY CRYSTAL-STRUCTURE OF ASCIDIACYCLAMIDE, A CYTOTOXIC CYCLIC PEPTIDE FROM ASCIDIAN [J].

ISHIDA, T ;

INOUE, M ;

HAMADA, Y ;

KATO, S ;

SHIOIRI, T .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (05) :370-371

[9]

Krimen L.I., 1969, ORGANIC REACTIONS NE, V17, P213, DOI DOI 10.1002/0471264180.0R017.03

[10]

Laphookhieo S, 2011, J BRAZIL CHEM SOC, V22, P176, DOI 10.1590/S0103-50532011000100024

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