Catalytic 1,2-Dicyanation of Alkynes by Palladium(II) under Aerobic Conditions

被引：27

作者：

Arai, Shigeru ^{[1
]}

Sato, Takashi ^{[1
]}

Nishida, Atsushi ^{[1
]}

机构：

[1] Chiba Univ, Grad Sch Pharmaceut Sci, Inage Ku, Chiba 2638522, Japan

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2009年 / 351卷 / 11-12期

关键词：

alkynes; cyanation; oxygen; palladium; CARBON TRIPLE BONDS; TRIMETHYLSILYL CYANIDE; STEREOSELECTIVE SYNTHESIS; TERMINAL ACETYLENES; OXIDATIVE ADDITION; C-C; NICKEL; ARYLCYANATION; ARYLACETYLENES; CYANATION;

D O I：

10.1002/adsc.200900334

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

A stereoselective 1,2-dicyanation of various alkynes in the presence of trimethylsilyl cyanide (TMSCN) by palladium(II) catalysis under aerobic conditions is investigated. This reaction includes two cyanation pathways, syn- and anti-cyanopalladation to alkynes that are activated by Pd(II). High syn-selectivity was observed in the reaction using terminal alkynes that have bulky substituents at a propargyl position and aliphatic internal alkynes. Furthermore, a dramatic acceleration was observed with substrates having an N-arenesulfonyl functionality at a propargyl position, this indicates that both sulfoxide and carbon-carbon triple bond act as Lewis bases to Pd(II).

引用

页码：1897 / 1904

页数：8

共 28 条

[11] Palladium-catalyzed three-component arylcyanation of internal alkynes-with aryl bromides and K4[Fe(CN)6] [J].

Cheng, Yi-nan ;

Duan, Zheng ;

Yu, Liujian ;

Li, Zhongxian ;

Zhu, Yu ;

Wu, Yangjie .

ORGANIC LETTERS, 2008, 10 (05) :901-904

[12] Synthesis of ethyl 3-cyano-2-methylcinnamates and 3-cyano-2-methylcinnamonitriles from the Baylis-Hillman acetates [J].

Chung, YM ;

Gong, JH ;

Kim, TH ;

Kim, JN .

TETRAHEDRON LETTERS, 2001, 42 (51) :9023-9026

[13] REGIO-CHEMICAL AND STEREO-CHEMICAL CONTROL IN THE NICKEL-CATALYZED ADDITION OF HCN TO ALKYNES - A SIMPLE SYNTHESIS OF (E)-2-ALKYL-3-TRIALKYLSILYLALK-2-ENENITRILES [J].

FALLON, GD ;

FITZMAURICE, NJ ;

JACKSON, WR ;

PERLMUTTER, P .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (01) :4-5

[14]

FUNABIKI T, 1978, J CHEM SOC CHEM COMM, V63

[15] A highly regioselective cyanothiolation of alkynes via oxidative addition of thiocyanates to tetrakis(triphenylphosphine)palladium(0) catalyst [J].

Kamiya, Ikuyo ;

Kawakami, Jun-ichi ;

Yano, Shigenobu ;

Nomoto, Akihiro ;

Ogawa, Akiya .

ORGANOMETALLICS, 2006, 25 (15) :3562-3564

[16] Palladium-catalyzed intramolecular cyanoamidation of alkynyl and alkenyl cyanoformamides [J].

Kobayashi, Yusuke ;

Kamisaki, Haruhi ;

Yanada, Reiko ;

Takemoto, Yoshiji .

ORGANIC LETTERS, 2006, 8 (13) :2711-2713

[17] Asymmetric Intramolecular Carbocyanation of Alkenes by C-C Bond Activation [J].

Najera, Carmen ;

Sansano, Jose M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (14) :2452-2456

[18] Nickel-catalyzed arylcyanation of alkynes [J].

Nakao, Y ;

Oda, S ;

Hiyama, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (43) :13904-13905

[19] Intramolecular arylcyanation of alkenes catalyzed by nickel/AlMe2CI [J].

Nakao, Yoshiaki ;

Ebata, Shiro ;

Yada, Akira ;

Hiyama, Tamejiro ;

Ikawa, Masashi ;

Ogoshi, Sensuke .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (39) :12874-+

[20] Hydroheteroarylation of alkynes under mild nickel catalysis [J].

Nakao, Yoshiaki ;

Kanyiva, Kyalo Stephen ;

Oda, Shinichi ;

Hiyama, Tamejiro .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (25) :8146-8147

← 1 2 3 →