Catalytic Dicyanative 5-exo- and 6-endo-Cyclization Triggered by Cyanopalladation of Alkynes

被引:22
作者
Arai, Shigeru [1 ]
Koike, Yuka [1 ]
Nishida, Atsushi [1 ]
机构
[1] Chiba Univ, Grad Sch Pharmaceut Sci, Inage Ku, Chiba 2638522, Japan
关键词
cyanation; cyanopalladation; cyclization; oxygen; palladium; TRIMETHYLSILYL CYANIDE; INTRAMOLECULAR CYANOBORATION; STEREOSELECTIVE-SYNTHESIS; OXIDATIVE ADDITION; C-C; PALLADIUM; CARBON; ARYLCYANATION; ACETYLENES; ALKENES;
D O I
10.1002/adsc.200900813
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
A stereoselective dicyanative 5-exo- and 6-endo-cyclization using various enynes has been investigated. The mode of cyclization is critically controlled by the structure of the substrates. For example, N-allyl derivatives prefer 5-exo-cyclization, while methacryloyl amides are transformed to the corresponding lactams with tetra-substituted carbons at the alpha-position via 6-endo-cyclization. Both reactions include syn-cyanopalladation to carbon carbon triple bonds in the initial step, and sequential cyclization followed by reductive elimination in one operation enables the construction of the highly functionalized nitrogen heterocycles. The scope of suitable substrates and a proposed mechanism are also described.
引用
收藏
页码:893 / 900
页数:8
相关论文
共 33 条
[1]  
[Anonymous], 2009, ANGEW CHEM, V121, P2488
[2]  
Arai S., 2009, ANGEW CHEM, V121, P4598
[3]   Catalytic 1,2-Dicyanation of Alkynes by Palladium(II) under Aerobic Conditions [J].
Arai, Shigeru ;
Sato, Takashi ;
Nishida, Atsushi .
ADVANCED SYNTHESIS & CATALYSIS, 2009, 351 (11-12) :1897-1904
[4]   Palladium-Catalyzed Cyanation of Carbon-Carbon Triple Bonds Under Aerobic Conditions [J].
Arai, Shigeru ;
Sato, Takashi ;
Koike, Yuka ;
Hayashi, Michino ;
Nishida, Atsushi .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (25) :4528-4531
[5]   C-C, C-O, C-N bond formation on sp2 carbon by Pd(II)-catalyzed reactions involving oxidant agents [J].
Beccalli, Egle M. ;
Broggini, Gianluigi ;
Martinelli, Michela ;
Sottocornola, Silvia .
CHEMICAL REVIEWS, 2007, 107 (11) :5318-5365
[6]   PALLADIUM-CATALYZED OR NICKEL-CATALYZED REACTION OF ALKYNES WITH TRIMETHYLSILYL CYANIDE - A NEW SYNTHESIS OF 5-AMINOPYRROLE-2-CARBONITRILES [J].
CHATANI, N ;
HANAFUSA, T .
TETRAHEDRON LETTERS, 1986, 27 (35) :4201-4204
[7]   PALLADIUM-CATALYZED ADDITION OF TRIMETHYLGERMYL CYANIDE TO TERMINAL ACETYLENES [J].
CHATANI, N ;
HORIUCHI, N ;
HANAFUSA, T .
JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (10) :3393-3395
[8]   ME3SICN .6. PALLADIUM-CATALYZED AND NICKEL-CATALYZED REACTION OF TRIMETHYLSILYL CYANIDE WITH ACETYLENES - ADDITION OF TRIMETHYLSILYL CYANIDE TO THE CARBON CARBON TRIPLE BONDS [J].
CHATANI, N ;
TAKEYASU, T ;
HORIUCHI, N ;
HANAFUSA, T .
JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (15) :3539-3548
[9]   PALLADIUM-CATALYZED ADDITION OF TRIMETHYLSILYL CYANIDE TO ARYLACETYLENES [J].
CHATANI, N ;
HANAFUSA, T .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (12) :838-839
[10]   PREPARATION OF VINYLGERMANES AND A GERMOLE BY THE PD-CATALYZED REACTIONS OF ME3GECN WITH ACETYLENES [J].
CHATANI, N ;
MORIMOTO, T ;
MUTO, T ;
MURAI, S .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1994, 473 (1-2) :335-342