Controlling diaza-cope rearrangement reactions with resonance-assisted hydrogen bonds

被引：49

作者：

Chin, J

Mancin, F

Thavarajah, N

Lee, DY

Lough, A

Chung, DS

机构：

[1] Dept Chem, Toronto, ON M5S 3H6, Canada

[2] Dept Chem, Toronto, ON M5S 3H6, Canada

[3] Seoul Natl Univ, Dept Chem, Seoul 151747, South Korea

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2003年 / 125卷 / 50期

关键词：

METAL COORDINATION; CRYSTAL-STRUCTURE;

D O I：

10.1021/ja0387554

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

NMR studies reveal that the equilibrium between 1 and 2 lies essentially toward 1 to the left without any detectable amount of 2. DFT computation shows that the value of K1 is about 1.4 × 10-5, and X-ray crystal structures show that the resonance-assisted hydrogen bond (RAHB) in 1 (1.66 Å) is shorter than the regular hydrogen bond in 2 (1.75 Å). The enormous selectivity can be explained in terms of the strength of the RAHBs in 1 compared to that of the regular hydrogen bonds in 2. Copyright © 2003 American Chemical Society.

引用

收藏

页码：15276 / 15277

页数：2

相关论文

共 19 条

[1] [1,2-BIS(2-HYDROXYPHENYL)ETHYLENEDIAMINE]DICHLOROPLATINUM(II), A NEW COMPOUND FOR THE THERAPY OF OVARIAN-CANCER .2. SYNTHESIS AND PRELIMINARY TESTING OF THE ENANTIOMERIC COMPLEXES [J].

BERNHARDT, G ;

GUST, R ;

REILE, H ;

VOMORDE, HD ;

MULLER, R ;

KELLER, C ;

SPRUSS, T ;

SCHONENBERGER, H ;

BURGEMEISTER, T ;

MANNSCHRECK, A ;

RANGE, KJ ;

KLEMENT, U .

JOURNAL OF CANCER RESEARCH AND CLINICAL ONCOLOGY, 1992, 118 (03) :201-208

[2] EVIDENCE FOR RESONANCE-ASSISTED HYDROGEN-BONDING .2. INTERCORRELATION BETWEEN CRYSTAL-STRUCTURE AND SPECTROSCOPIC PARAMETERS IN 8 INTRAMOLECULARLY HYDROGEN-BONDED 1,3-DIARYL-1,3-PROPANEDIONE ENOLS [J].

BERTOLASI, V ;

GILLI, P ;

FERRETTI, V ;

GILLI, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (13) :4917-4925

[3] Synergistic effect between metal coordination and hydrogen bonding in phosphate and halide recognition [J].

Chin, J ;

Chung, S ;

Kim, DH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (37) :10948-10949

[4] LOW-BARRIER HYDROGEN-BONDS AND ENZYMATIC CATALYSIS [J].

CLELAND, WW ;

KREEVOY, MM .

SCIENCE, 1994, 264 (5167) :1887-1890

[5] A simplified synthesis of (+/-)-1,2-diphenyl-1,2-diaminoethane (1) from benzaldehyde and ammonia. Revision of the structures of the long-known intermediates ''hydrobenzamide'' and ''amarine'' [J].

Corey, EJ ;

Kuhnle, FNM .

TETRAHEDRON LETTERS, 1997, 38 (50) :8631-8634

[6] Low barrier hydrogen bonds in sterically modified Schiff bases [J].

Filarowski, A ;

Koll, A ;

Glowiak, T .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2002, (04) :835-842

[7] A LOW-BARRIER HYDROGEN-BOND IN THE CATALYTIC TRIAD OF SERINE PROTEASES [J].

FREY, PA ;

WHITT, SA ;

TOBIN, JB .

SCIENCE, 1994, 264 (5167) :1927-1930

[8] EVIDENCE FOR RESONANCE-ASSISTED HYDROGEN-BONDING FROM CRYSTAL-STRUCTURE CORRELATIONS ON THE ENOL FORM OF THE BETA-DIKETONE FRAGMENT [J].

GILLI, G ;

BELLUCCI, F ;

FERRETTI, V ;

BERTOLASI, V .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (03) :1023-1028

[9] Evidence for intramolecular N-H•••O resonance-assisted hydrogen bonding in β-enaminones and related heterodienes.: A combined crystal-structural, IR and NMR spectroscopic, and quantum-mechanical investigation [J].

Gilli, P ;

Bertolasi, V ;

Ferretti, V ;

Gilli, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (42) :10405-10417

[10]

Guthrie JP, 1996, CHEM BIOL, V3, P163