Selective meta-deprotonation of toluene by using alkali-metal-mediated magnesiation

被引：74

作者：

Andrikopoulos, PC ^{[1
]}

Armstrong, DR ^{[1
]}

Graham, DV ^{[1
]}

Hevia, E ^{[1
]}

Kennedy, AR ^{[1
]}

Mulvey, RE ^{[1
]}

O'Hara, CT ^{[1
]}

Talmard, C ^{[1
]}

机构：

[1] Univ Strathclyde, Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 22期

关键词：

deprotonation; inverse crown compounds; magnesium; metalation; sodium;

D O I：

10.1002/anie.200500379

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Back to bases: Conventional organometallic bases usually deprotonate toluene at the methyl position to generate resonance-stabilized benzyl anions, but using a new type of bimetallic metalation, sodium-mediated magnesiation, the thermodynamic position for deprotonation can be switched to the aromatic ring (see picture). (Chemical Equation Presented) © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：3459 / 3462

页数：4

共 20 条

[1] A homologous series of regioselectively tetradeprotonated group 8 metallocenes: New inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base [J].

Andrikopoulos, PC ;

Armstrong, DR ;

Clegg, W ;

Gilfillan, CJ ;

Hevia, E ;

Kennedy, AR ;

Mulvey, RE ;

O'Hara, CT ;

Parkinson, JA ;

Tooke, DM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (37) :11612-11620

[2]

[Anonymous], 1999, ANGEW CHEM, V111, P231

[3]

Armstrong DR, 1999, ANGEW CHEM INT EDIT, V38, P131, DOI 10.1002/(SICI)1521-3773(19990115)38:1/2<131::AID-ANIE131>3.0.CO

[4]

2-9

[5] Deprotonation of fluoro aromatics using lithium magnesates [J].

Awad, H ;

Mongin, F ;

Trécourt, F ;

Quéguiner, G ;

Marsais, F ;

Blanco, F ;

Abarca, B ;

Ballesteros, R .

TETRAHEDRON LETTERS, 2004, 45 (36) :6697-6701

[6] HOMOGENEOUS METALATION OF ALKYLBENZENES [J].

BROADDUS, CD .

JOURNAL OF ORGANIC CHEMISTRY, 1970, 35 (01) :10-&

[7] METALATION OF TOLUENE . QUESTION OF KINETIC VS THERMODYNAMIC CONTROL [J].

BROADDUS, CD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (18) :4174-&

[8] RING METALATION OF TOLUENE BY BUTYLLITHIUM IN PRESENCE OF N,N,N=,N=-TETRAMETHYLETHYLENEDIAMINE [J].

CHALK, AJ ;

HOOGEBOO.TJ .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1968, 11 (03) :615-&

[9]

ELSCHENBROICH C, 1992, ORGANOMETALLICS CONC, P6

[10] Isolation and characterisation of the mixed-metal alkyl amide [(TMEDA)Na(μ-Bu)(μ-TMP)Mg(TMP)], an unexpected chelate-trapped intermediate in the formation of inverse crowns [J].

Hevia, E ;

Gallagher, DJ ;

Kennedy, AR ;

Mulvey, RE ;

O'Hara, CT ;

Talmard, C .

CHEMICAL COMMUNICATIONS, 2004, (21) :2422-2423

← 1 2 →