Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Alkynes through C-H Activation

被引：26
作者：
Kawaguchi, Yasuaki [1 ]
Yasuda, Shigeo [1 ]
Kaneko, Akira [1 ]
Oura, Yuki [1 ]
Mukai, Chisato [1 ]
机构：
[1] Kanazawa Univ, Grad Sch Med Sci, Div Pharmaceut Sci, Kanazawa, Ishikawa 9201192, Japan
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 29期
关键词：
alkynes; allenes; C-H activation; cycloisomerization; rhodium; CATALYZED 5+2 CYCLOADDITIONS; BOND ACTIVATION; VINYLCYCLOPROPANES; ALLENYNES; 1ST; SELECTIVITY; CYCLIZATION; COMPLEXES; CHIRALITY; ALKENES;
D O I：
10.1002/anie.201403990
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The efficient Rh-I-catalyzed cycloisomerization of benzylallene-alkynes produced the tricyclo[9.4.0.0(3,8)]pentadecapentaene skeleton through a C-sp2-H bond activation in good yields. A plausible reaction mechanism proceeds via oxidative addition of the acetylenic C-H bond to Rh-I, an enetype cyclization to the vinylidenecarbene-Rh-I intermediate, and an electrophilic aromatic substitution with the vinylidenecarbene species. It was proposed based on deuteration and competition experiments.
引用
收藏
页码：7608 / 7612
页数：5
相关论文
共 73 条
[1]   Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope [J].
Ackermann, Lutz .
CHEMICAL REVIEWS, 2011, 111 (03) :1315-1345
[2]   Transition-Metal-Catalyzed Rearrangements of Small Cycloalkanes: Regioselectivity Trends in β-Carbon Elimination Reactions [J].
Aissa, Christophe .
SYNTHESIS-STUTTGART, 2011, (21) :3389-3407
[3]   Transition Metal Catalyzed Cycloisomerizations of 1,n-Allenynes and -Allenenes [J].
Aubert, Corinne ;
Fensterbank, Louis ;
Garcia, Pierre ;
Malacria, Max ;
Simonneau, Antoine .
CHEMICAL REVIEWS, 2011, 111 (03) :1954-1993
[4]   Synthesis of functionalized resorcinols by rhodium-catalyzed [5+1] cycloaddition reaction of 3-acyloxy-1,4-enynes with CO [J].
Brancour, Celia ;
Fukuyama, Takahide ;
Ohta, Yuko ;
Ryu, Ilhyong ;
Dhimane, Anne-Lise ;
Fensterbank, Louis ;
Malacria, Max .
CHEMICAL COMMUNICATIONS, 2010, 46 (30) :5470-5472
[5]   A rhodium(I)-catalyzed formal allenic Alder ene reaction for the rapid and stereoselective assembly of cross-conjugated trienes [J].
Brummond, KM ;
Chen, HF ;
Sill, P ;
You, LF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (51) :15186-15187
[6]   Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation [J].
Colby, Denise A. ;
Bergman, Robert G. ;
Ellman, Jonathan A. .
CHEMICAL REVIEWS, 2010, 110 (02) :624-655
[7]  
Crepin D., 2010, ANGEW CHEM, V122, P630
[8]   Combined Rhodium-Catalyzed Carbon-Hydrogen Activation and β-Carbon Elimination to access Eight-Membered Rings [J].
Crepin, Damien ;
Dawick, James ;
Aissa, Christophe .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (03) :620-623
[9]   Palladium- and Copper-Catalyzed Arylation of Carbon-Hydrogen Bonds [J].
Daugulis, Olafs ;
Do, Hien-Quang ;
Shabashov, Dmitry .
ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (08) :1074-1086
[10]  
Dyker G, 2005, HANDBOOK OF C-H TRANSFORMATIONS: APPLICATIONS IN ORGANIC SYNTHESIS, VOL 1, pV
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