A unique approach to metal-induced Bergman cyclization: Long-range enediyne activation by ligand-to-metal charge transfer

被引：28

作者：

Bhattacharyya, S ^{[1
]}

Pink, M ^{[1
]}

Baik, MH ^{[1
]}

Zaleski, JM ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 04期

关键词：

D O I：

10.1002/anie.200461825

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Dramatic differences are found in the temperatures at which Bergman cyclizations occur when MoIV-enedithiolate-enediyne complexes are used (see scheme; S: yellow, Mo: red), and this can be directly attributed to a long-range electronic polarization effect of the metal center. Ligand-to-metal charge transfer within the C2S4 substructure and differential charge repulsion in the transition state lead to a lowering of the barrier to cyclization.

引用

页码：592 / 595

页数：4

共 17 条

[1] Reactant destabilization in the Bergman cyclization and rational design of light- and pH-activated enediynes [J].

Alabugin, IV ;

Manoharan, M .

JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (18) :3363-3371

[2] Tuning rate of the Bergman cyclization of benzannelated enediynes with ortho substituents [J].

Alabugin, IV ;

Manoharan, M ;

Kovalenko, SV .

ORGANIC LETTERS, 2002, 4 (07) :1119-1122

[3] Stereoelectronic effects and general trends in hyperconjugative acceptor ability of σ bonds [J].

Alabugin, IV ;

Zeidan, TA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (12) :3175-3185

[4] Synthesis and thermal reactivity of a novel macrocyclic enediyne and its copper(II) complex [J].

Basak, A ;

Shain, JC .

TETRAHEDRON LETTERS, 1998, 39 (19) :3029-3030

[5] Metalloenediynes: Ligand field control of thermal Bergman cyclization reactions [J].

Benites, PJ ;

Rawat, DS ;

Zaleski, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (30) :7208-7217

[6] Isolation of electronic from geometric contributions to Bergman cyclization of metalloenediynes [J].

Bhattacharyya, S ;

Clark, AE ;

Pink, M ;

Zaleski, JM .

CHEMICAL COMMUNICATIONS, 2003, (10) :1156-1157

[7] Bergman, aza-Bergman, and protonated aza-Bergman cyclizations and intermediate 2,5-arynes: Chemistry and challenge to computation [J].

Cramer, CJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (25) :6261-6269

[8] Benzannelation alters the rate limiting step in enediyne cycloaromatization [J].

Kaneko, T ;

Takahashi, M ;

Hirama, M .

TETRAHEDRON LETTERS, 1999, 40 (10) :2015-2018

[9] COMPARISON OF BIRADICAL FORMATION BETWEEN ENEDIYNE AND ENYNE ALLENE - ABINITIO CASSCF AND MRSDCI STUDY [J].

KOGA, N ;

MOROKUMA, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (06) :1907-1911

[10] Synthesis, structure, and reactivity of enediyne macrocycles [J].

Konig, B ;

Pitsch, W ;

Thondorf, I .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (13) :4258-4261

← 1 2 →