Aggregative activation in heterocyclic chemistry .4. Metallation of 2-methoxypyridine: unusual behaviour of the new unimetal superbase BuLi-Me2N(CH2)(2)OLi (BuLi-LiDMAE)

被引：60

作者：

Gros, P ^{[1
]}

Fort, Y ^{[1
]}

Caubere, P ^{[1
]}

机构：

[1] UNIV NANCY 1,FAC SCI,LAB CHIM ORGAN 1,CNRS,URA 457,F-54506 VANDOEUVRE NANCY,FRANCE

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1997年 / 20期

关键词：

D O I：

10.1039/a701914i

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of potential unimetal superbases BuLi-ROLi has been studied in order to increase the basicity/ nucleophilicity ratio ([B/N]R) of BuLi, The best [B/N]R ratio is found with BuLi-LiDMAE, This complex base apparently metallates 2-methoxypyridine at the unexpected Cd position, It is shown that no actual metallated species are formed in the reaction medium, the reaction occurring as the result of a common radical precursor stabilized by an aggregate cluster. Finally, as an application, Ca substituted 2-methoxypyridines have been obtained in good to excellent yields.

引用

页码：3071 / 3080

页数：10

共 47 条

[31] INTERACTION OF ALKYL LITHIUM COMPOUNDS WITH LITHIUM ALCOHOLATES [J].

LOCHMANN, L ;

POSPISIL, J ;

VODNANSK.J ;

TREKOVAL, J ;

LIM, D .

COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 1965, 30 (07) :2187-&

[32] PREPARATION AND PROPERTIES OF PURE LITHIO ESTERS OF SOME CARBOXYLIC-ACIDS [J].

LOCHMANN, L ;

LIM, D .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1973, 50 (01) :9-16

[33] Lithium ion solvation: Amine and unsaturated hydrocarbon solvates of lithium hexamethyldisilazide (LiHMDS) [J].

Lucht, BL ;

Collum, DB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (09) :2217-2225

[34] ENANTIOSELECTIVE FORMATION OF CIS-3,5-DIMETHYLCYCLOHEXANONE LITHIUM ENOLATE AND STEREOSELECTIVE ALDOL REACTION WITH BENZALDEHYDE [J].

MAJEWSKI, M ;

GLEAVE, DM .

JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (13) :3599-3605

[35] [NORMAL-BULI.LIOTBU]4, SOLID-STATE STRUCTURE OF AN NORMAL-BUTYLLITHIUM LITHIUM TERT-BUTOXIDE COMPLEX [J].

MARSCH, M ;

HARMS, K ;

LOCHMANN, L ;

BOCHE, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1990, 29 (03) :308-309

[36] HIGH-FIELD H-1-NMR STUDY OF THE AGGREGATION AND COMPLEXATION OF NORMAL-BUTYLLITHIUM IN TETRAHYDROFURAN [J].

MCGARRITY, JF ;

OGLE, CA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (07) :1805-1810

[37] MELDOLA MEDAL LECTURE - RING-STACKING AND RING-LADDERING IN ORGANONITROGENLITHIUM COMPOUNDS - THE DEVELOPMENT OF CONCEPTS WITH WIDE APPLICABILITY THROUGHOUT LITHIUM STRUCTURAL CHEMISTRY [J].

MULVEY, RE .

CHEMICAL SOCIETY REVIEWS, 1991, 20 (02) :167-209

[38] COMPLEX BASES .10. NEW COMPLEX BASES - APPLICATION TO SOLUTION ANIONIC-POLYMERIZATION OF VINYL MONOMERS [J].

NDEBEKA, G ;

CAUBERE, P ;

RAYNAL, S ;

LECOLIER, S .

POLYMER, 1981, 22 (03) :347-355

[39]

NEWKOME G, 1982, J ORG CHEM, V47, P600

[40]

PERDICAKIS M, 1982, C R ACAD SCI PARIS 2, P879

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