Enzymelike Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation

被引:296
作者
Hastings, Courtney J.
Pluth, Michael D.
Bergman, Robert G. [1 ]
Raymond, Kenneth N.
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
关键词
CHEMISTRY; REARRANGEMENTS; DERIVATIVES; COMPLEXES; CAVITY; GUESTS; RATES;
D O I
10.1021/ja102633e
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The water-soluble, self-assembled, tetrahedral assembly K12Ga4L6 (L = 1,5-biscatecholamidenaphthalene) catalyzes the Nazarov cyclization of 1,3-pentadienols with extremely high levels of efficiency. The catalyzed reaction proceeds over a million times faster than the background reaction, an increase comparable to those observed in some enzymatic systems. This catalysis operates under aqueous conditions at mild temperatures and pH, and the reaction is halted by the addition of an appropriate inhibitor. This unprecedented rate enhancement is attributed to both the stabilization of protonated reaction intermediates and the effect of constrictive binding on the bound guest.
引用
收藏
页码:6938 / +
页数:4
相关论文
共 33 条
[11]  
2-G
[12]  
Jencks W.P., 1969, Catalysis in Chemistry and Enzymology
[13]   Diels-Alder reactions through reversible encapsulation [J].
Kang, JM ;
Hilmersson, G ;
Santamaría, J ;
Rebek, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (15) :3650-3656
[14]   ORGANOMETALLIC CHEMISTRY OF TRANSITION METALS .21. SOME PI-PENTAMETHYLCYCLOPENTADIENYL DERIVATIVES OF VARIOUS TRANSITION METALS [J].
KING, RB ;
BISNETTE, MB .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1967, 8 (02) :287-+
[15]  
Kirby AJ, 1996, ANGEW CHEM INT EDIT, V35, P707
[16]   Very high rate enhancement of benzyl alcohol oxidation by an artificial enzyme [J].
Marinescu, Lavinia G. ;
Bols, Mikael .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (28) :4590-4593
[17]   CATALYSIS BY CURCURBITURIL - THE SIGNIFICANCE OF BOUND-SUBSTRATE DESTABILIZATION FOR INDUCED TRIAZOLE FORMATION [J].
MOCK, WL ;
IRRA, TA ;
WEPSIEC, JP ;
ADHYA, M .
JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (22) :5302-5308
[18]   Unusual [2+4] and [2+2] cycloadditions of arenes in the confined cavity of self-assembled cages [J].
Nishioka, Yuki ;
Yamaguchi, Takumi ;
Yoshizawa, Michito ;
Fujita, Makoto .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (22) :7000-+
[19]   Self-Organization in Coordination-Driven Self-Assembly [J].
Northrop, Brian H. ;
Zheng, Yao-Rong ;
Chi, Ki-Whan ;
Stang, Peter J. .
ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (10) :1554-1563
[20]   Supramolecular chemistry in water [J].
Oshovsky, Gennady V. ;
Reinhoudt, David N. ;
Verboom, Willem .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (14) :2366-2393