Reaction of magnesiated bases on substituted pyridines:: deprotonation or 1,4-addition?

被引：16

作者：

Bonnet, V ^{[1
]}

Mongin, F ^{[1
]}

Trécourt, F ^{[1
]}

Quéguiner, G ^{[1
]}

机构：

[1] IRCOF, Lab Chim Organ Fine & Heterocycl, UMR 6014, F-76131 Mt St Aignan, France

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 2000年 / 24期

关键词：

D O I：

10.1039/b007270m

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

N-(tert-Butyl)pyridine-2-carboxamide (1), N-phenylpyridine-2-carboxamide (7) and 2,2-dimethyl-N-(2-pyridyl)propanamide (18) are readily deprotonated at C3 with a stoichiometric amount of (PrMgCl)-Mg-i or Bu2Mg in THF under reflux. Subsequent trapping with various electrophiles (deuterated water, aldehydes, iodine and dimethyl disulfide) gives 2,3-disubstituted pyridines carrying a useful carboxylic acid- or amino-derived function at C2. When N-(tert-butyl)pyridine-3-carboxamide (12) and 2,2-dimethyl-N-(3-pyridyl)propanamide (22) are subjected to the same reaction conditions, 1,4-addition to the pyridine ring occurs, giving 4-alkyl derivatives. Starting from N-(tert-butyl)pyridine-4-carboxamide (15), 1,2-addition and deprotonation reactions occur simultaneously.

引用

页码：4245 / 4249

页数：5

共 22 条

[1] Optically active transition metal complexes .110. New rhodium(I) complexes with 2-pyridinecarboxamido ligands
Brunner, H
Nuber, B
Prommesberger, M
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 523 (02) : 179 - 185
[2] MAGNESIUM AMIDE BASES AND AMIDO-GRIGNARDS .1. ORTHO-MAGNESIATION
EATON, PE
LEE, CH
XIONG, YH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (20) : 8016 - 8018
[3] EPSZTAJN J, 1986, J CHEM RES-S, P20
[4] APPLICATION OF ORGANO-LITHIUM AND RELATED REAGENTS IN SYNTHESIS .2. THE DUAL BEHAVIOR OF N,N-DIALKYLPYRIDYLCARBOXYLIC AMIDES IN THE REACTION WITH LITHIUM DIISOPROPYLAMIDE
EPSZTAJN, J
BIENIEK, A
BRZEZINSKI, JZ
JOZWIAK, A
[J]. TETRAHEDRON LETTERS, 1983, 24 (43) : 4735 - 4738
[5] Epsztajn J., 1986, J CHEM RES M, P442
[6] METALATION SRN1 COUPLING IN HETEROCYCLIC SYNTHESIS - A CONVENIENT METHODOLOGY FOR RING FUNCTIONALIZATION
ESTEL, L
MARSAIS, F
QUEGUINER, G
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (12) : 2740 - 2744
[7] GU YG, 1999, BIOORG MED CHEM LETT, P1431
[8] GUNGOR T, 1982, SYNTHESIS-STUTTGART, P499
[9] HOUGHTON RP, 1967, TETRAHEDRON LETT, P3929
[10] Magnesiation of indoles with magnesium amide bases
Kondo, Y
Yoshida, A
Sakamoto, T
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1996, (19): : 2331 - 2332

← 1 2 3 →