N-aryl pyrazoles: DFT calculations of CH acidity and deprotonative metallation using a combination of lithium and zinc amides

被引：48

作者：

Chevallier, Floris ^{[1
]}

Halauko, Yury S. ^{[2
]}

Pecceu, Christelle ^{[1
]}

Nassar, Ibrahim F. ^{[1
]}

Dam, To Uyen ^{[1
]}

Roisnel, Thierry ^{[3
]}

Matulis, Vadim E. ^{[4
]}

Ivashkevich, Oleg A. ^{[4
]}

Mongin, Florence ^{[1
]}

机构：

[1] Univ Rennes 1, UMR 6510, CNRS, F-35042 Rennes, France

[2] Belarusian State Univ, Dept Electrochem, Minsk 220030, BELARUS

[3] Univ Rennes 1, CNRS, Ctr Diffractometrie 10, UMR 6226, F-35042 Rennes, France

[4] Belarusian State Univ, Res Inst Physicochem Problems, Minsk 220030, BELARUS

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2011年 / 9卷 / 12期

关键词：

MEDIATED ZINCATION; ORTHO-LITHIATION; 1-PHENYLPYRAZOLE; CHEMISTRY; ARYLATION; LIGANDS; HALIDES;

D O I：

10.1039/c1ob05267e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of N-aryl and N-heteroaryl pyrazoles have been deproto-metallated using a 2,2,6,6-tetramethylpiperidino-based mixed lithium-zinc combination. Mono-, di-, and tri-iodides have been obtained after subsequent trapping with iodine, depending on the substrate and on the quantity of base used. The results have been discussed in the light of the CH acidities of the substrates, determined both in the gas phase and in THF solution using the DFT B3LYP method.

引用

页码：4671 / 4684

页数：14

共 54 条

[1] THE METALATION OF 1-PHENYLPYRAZOLE AND 1-METHYLPYRAZOLE WITH NORMAL-BUTYLLITHIUM [J].

ALLEY, PW ;

SHIRLEY, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (23) :6271-6274

[2] SIR97:: a new tool for crystal structure determination and refinement [J].

Altomare, A ;

Burla, MC ;

Camalli, M ;

Cascarano, GL ;

Giacovazzo, C ;

Guagliardi, A ;

Moliterni, AGG ;

Polidori, G ;

Spagna, R .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 :115-119

[3]

[Anonymous], 2002, ORGANOMETALLICS SYNT

[4] Directed meta-metalation using alkali-metal-mediated zincation [J].

Armstrong, David R. ;

Clegg, William ;

Dale, Sophie H. ;

Hevia, Eva ;

Hogg, Lorna M. ;

Honeyman, Gordon W. ;

Mulvey, Robert E. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (23) :3775-3778

[5] Ruthenium- and rhodium-catalyzed direct carbonylation of the ortho C-H bond in the benzene ring of N-arylpyrazoles [J].

Asaumi, T ;

Matsuo, T ;

Fukuyama, T ;

Ie, Y ;

Kakiuchi, F ;

Chatani, N .

JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (13) :4433-4440

[6] EQUILIBRIUM CH ACIDITY OF ACETYLENIC DERIVATIVES OF N-ALKYLAZOLES IN DMSO [J].

BELOV, AI ;

TEREKHOVA, MI ;

PETROV, ES ;

VASILEVSKII, SF ;

SHVARTSBERG, MS .

BULLETIN OF THE RUSSIAN ACADEMY OF SCIENCES-DIVISION OF CHEMICAL SCIENCE, 1992, 41 (03) :398-402

[7] Metalation of nitroaromatics with in situ electrophiles [J].

Black, WC ;

Guay, B ;

Scheuermeyer, F .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (03) :758-760

[8] A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics [J].

Cances, E ;

Mennucci, B ;

Tomasi, J .

JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (08) :3032-3041

[9] Efficient nucleophilic substitution reactions of pyrimidyl and pyrazyl halides with nucleophiles, under focused microwave irradiation [J].

Cherng, YH .

TETRAHEDRON, 2002, 58 (05) :887-890

[10] Trifluoromethyl-substituted pyridyl- and pyrazolylboronic acids and esters: synthesis and Suzuki-Miyaura cross-coupling reactions [J].

Clapham, Kate M. ;

Batsanov, Andrei S. ;

Bryce, Martin R. ;

Tarbit, Brian .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2009, 7 (10) :2155-2161

← 1 2 3 4 5 6 →