P. Caubère, Unimetal super bases, Chemical Reviews, vol.93, issue.6, pp.2317-2334, 1993.
DOI : 10.1021/cr00022a012

S. H. Wunderlich and P. Knochel, (tmp)2Zn???2???MgCl2???2???LiCl: A Chemoselective Base for the Directed Zincation of Sensitive Arenes and Heteroarenes, Angewandte Chemie International Edition, vol.37, issue.40, pp.7685-7688, 2007.
DOI : 10.1002/anie.200701984

M. Mosrin and P. Knochel, TMPZnCl??LiCl: A New Active Selective Base for the Directed Zincation of Sensitive Aromatics and Heteroaromatics, Organic Letters, vol.11, issue.8, pp.1837-1840, 2009.
DOI : 10.1021/ol900342a

S. H. Wunderlich and P. Knochel, Aluminum Bases for the Highly Chemoselective Preparation of Aryl and Heteroaryl Aluminum Compounds, Angewandte Chemie International Edition, vol.24, issue.8, pp.1501-1504, 2009.
DOI : 10.1002/anie.200804966

J. Garcia-Álvarez, A. R. Kennedy, J. Klett, and R. E. Mulvey, Alkali-Metal-Mediated Manganation: A Method for Directly Attaching Manganese(II) Centers to Aromatic Frameworks, Angewandte Chemie International Edition, vol.45, issue.7, pp.1105-1108, 2007.
DOI : 10.1002/anie.200604542

S. Usui, Y. Hashimoto, J. V. Morey, A. E. Wheatley, and M. Uchiyama, Cupration:?? A New Route to Regioselectively Functionalized Aromatics, Journal of the American Chemical Society, vol.129, issue.49, pp.15102-15103, 2007.
DOI : 10.1021/ja074669i

T. T. Nguyen, F. Chevallier, V. Jouikov, and F. Mongin, New Gilman-type lithium cuprate from a copper(II) salt: synthesis and deprotonative cupration of aromatics, Tetrahedron Letters, vol.50, issue.49, pp.6787-6790, 2009.
DOI : 10.1016/j.tetlet.2009.09.100

R. R. Fraser and T. S. Mansour, The effect of additives on organolithiums, Tetrahedron Letters, vol.27, issue.3, pp.331-334, 1986.
DOI : 10.1016/S0040-4039(00)84010-1

S. Hauptmann and A. Speicher, R. in Handbook of Heterocyclic Chemistry, 1 st ed.; Pergamon, The Chemistry of Heterocycles, 1985.

P. D. Rao, B. J. Littler, I. Geier, G. R. Lindsey, and J. S. , -Porphyrins, The Journal of Organic Chemistry, vol.65, issue.4, pp.1084-1092, 2000.
DOI : 10.1021/jo9915473
URL : https://hal.archives-ouvertes.fr/hal-00159700

F. M. Piller and P. Knochel, Regio- and Chemoselective Synthesis of Fully Substituted Thiophenes, Organic Letters, vol.11, issue.2, pp.445-448, 2009.
DOI : 10.1021/ol802513q

A. Krasovskiy, V. Krasovskaya, and P. Knochel, Mixed Mg/Li Amides of the Type R2NMgCl???LiCl as Highly Efficient Bases for the Regioselective Generation of Functionalized Aryl and Heteroaryl Magnesium Compounds, Angewandte Chemie International Edition, vol.68, issue.18, pp.2958-2961, 2006.
DOI : 10.1002/anie.200504024

W. Clegg, S. H. Dale, E. Hevia, L. M. Hogg, G. W. Honeyman et al., Alkali-Metal-Mediated Zincation of Polycyclic Aromatic Hydrocarbons: Synthesis and Structures of Mono- and Dizincated Naphthalenes, Dimetallated species have been previously described using zincate or manganate type bases, pp.6548-6550, 2006.
DOI : 10.1002/anie.200602288

G. Quéguiner, F. Marsais, V. Snieckus, and J. Epsztajn, Directed Metalation of Pi-Deficient Azaaromatics: Strategies of Functionalization of Pyridines, Quinolines, and Diazines, Adv. Heterocycl. Chem, vol.52, pp.187-304, 1991.
DOI : 10.1016/S0065-2725(08)60965-4

F. Mongin and G. Quéguiner, Advances in the directed metallation of azines and diazines (pyridines, pyrimidines, pyrazines, pyridazines, quinolines, benzodiazines and carbolines). Part 1: Metallation of pyridines, quinolines and carbolines, Tetrahedron, vol.57, issue.19, pp.4059-4090, 2001.
DOI : 10.1016/S0040-4020(01)00100-4

H. Awad, F. Mongin, F. Trécourt, G. Quéguiner, and F. Marsais, Deprotonation of chloropyridines using lithium magnesates, Tetrahedron Letters, vol.45, issue.42, pp.7873-7877, 2004.
DOI : 10.1016/j.tetlet.2004.08.151

P. Gros, S. Choppin, J. Mathieu, and Y. Fort, Lithiation of 2-Heterosubstituted Pyridines with BuLi???LiDMAE:?? Evidence for Regiospecificity at C-6, The Journal of Organic Chemistry, vol.67, issue.1, pp.234-237, 2002.
DOI : 10.1021/jo015855o

T. D. Krizan and J. C. Martin, Directed ortho lithiation of isophthalonitrile. New methodology for the synthesis of 1,2,3-trisubstituted benzenes, The Journal of Organic Chemistry, vol.47, issue.13, pp.2681-2682, 1982.
DOI : 10.1021/jo00134a038

A. A. Pletnev, Q. Tian, and R. C. Larock, Carbopalladation of Nitriles:?? Synthesis of 2,3-Diarylindenones and Polycyclic Aromatic Ketones by the Pd-Catalyzed Annulation of Alkynes and Bicyclic Alkenes by 2-Iodoarenenitriles, The Journal of Organic Chemistry, vol.67, issue.26, pp.9276-9287, 2002.
DOI : 10.1021/jo026178g

F. Fabis, S. Lemaître, A. Bouillon, S. Rault, T. Cailly et al., Butyllithium in a mixture of THF and hexane has also been used, albeit in a low yield, to metallate 4-cyanopyridine at the 2 position: (f) Su, Tetrahedron Lett, vol.46, pp.135-137, 2005.

G. C. Clososki, C. J. Rohbogner, and P. Knochel, Direct Magnesiation of Polyfunctionalized Arenes and Heteroarenes Using (tmp)2Mg???2???LiCl, Angewandte Chemie International Edition, vol.56, issue.40, pp.7681-7684, 2007.
DOI : 10.1002/anie.200701487

G. Bentabed-ababsa, F. Blanco, A. Derdour, F. Mongin, F. Trécourt et al., ]pyridines, The Journal of Organic Chemistry, vol.74, issue.1, pp.163-169, 2009.
DOI : 10.1021/jo801675h
URL : https://hal.archives-ouvertes.fr/hal-01290443

G. Jones, The chemistry of the triazolopyridines: an update, Adv. Heterocycl. Chem, vol.83, pp.1-70, 2002.
DOI : 10.1016/S0065-2725(02)83003-3

G. Jones, D. J. Mouat, and M. A. Pitman, Triazolopyridines. 16 1. lithiation of 3-cyano[1,2,3]triazolo[1,5-a]-pyridine, Tetrahedron, vol.51, issue.40, pp.10969-10978, 1995.
DOI : 10.1016/0040-4020(95)00652-O

N. Plé, A. Turck, K. Couture, and G. Quéguiner, Diazines 13: Metalation without Ortho-Directing Group - Functionalization of Diazines via Direct Metalation, The Journal of Organic Chemistry, vol.60, issue.12, pp.3781-3786, 1995.
DOI : 10.1021/jo00117a033

T. Imahori and Y. Kondo, -Bu-P4 Base, Journal of the American Chemical Society, vol.125, issue.27, pp.8082-8083, 2003.
DOI : 10.1021/ja0342300
URL : https://hal.archives-ouvertes.fr/jpa-00244326

K. Pieterse, A. Lauritsen, A. P. Schenning, J. A. Vekemans, and E. W. Meijer, Symmetrical Electron-Deficient Materials Incorporating Azaheterocycles, Chemistry - A European Journal, vol.9, issue.22, pp.5597-5604, 2003.
DOI : 10.1002/chem.200305073
URL : http://repository.tue.nl/587731

R. C. Ellingson and R. L. Henry, Pyrazine Chemistry. IV. Bromination of 2-Amino-3-carbomethoxypyrazine, Journal of the American Chemical Society, vol.71, issue.8, pp.2798-2800, 1949.
DOI : 10.1021/ja01176a058

T. Itoh, S. Kato, N. Nonoyama, T. Wada, K. Maeda et al., Efficient Synthesis of a Highly Selective NPY-5 Receptor Antagonist:?? A Drug Candidate for the Treatment of Obesity, Organic Process Research & Development, vol.10, issue.4, pp.822-828, 2006.
DOI : 10.1021/op0600963

R. Saito, S. Machida, and S. Suzuki, For recent examples, see: (a)

M. Mosrin, N. Boudet, and P. Knochel, Regio- and chemoselective magnesiation of protected uracils and thiouracils using TMPMgCl??LiCl and TMP2Mg??2LiCl, Organic & Biomolecular Chemistry, vol.53, issue.18, pp.3237-3239, 2008.
DOI : 10.1039/b812528g

G. Dayaker, A. Sreeshailam, F. Chevallier, T. Roisnel, P. Krishna et al., Deprotonative metallation of ferrocenes using mixed lithium???zinc and lithium???cadmium combinations, Chemical Communications, vol.11, issue.16, pp.2862-2864, 2010.
DOI : 10.1039/b924939g
URL : https://hal.archives-ouvertes.fr/hal-00738773

N. Long, Organometallic Compounds for Nonlinear Optics???The Search for En-light-enment!, Angewandte Chemie International Edition in English, vol.34, issue.1, pp.21-38, 1995.
DOI : 10.1002/anie.199500211

D. R. Van-staveren and N. Metzler-nolte, Bioorganometallic Chemistry of Ferrocene, Chemical Reviews, vol.104, issue.12, pp.5931-5986, 2004.
DOI : 10.1021/cr0101510

R. C. Atkinson, V. C. Gibson, and N. Long, The syntheses and catalytic applications of unsymmetrical ferrocene ligands, Chemical Society Reviews, vol.33, issue.5, pp.313-328, 2004.
DOI : 10.1039/b316819k

A. H. Stoll, P. Mayer, and P. Knochel, Preparation of Di-, Tri-, and Tetra-Substituted Functionalized Ferrocenes via Magnesium Organometallics, Organometallics, vol.26, issue.27, pp.6694-6697, 2007.
DOI : 10.1021/om701046c

R. Sanders and U. T. Mueller-westerhoff, The lithiation of ferrocene and ruthenocene: a retraction and an improvement, Journal of Organometallic Chemistry, vol.512, issue.1-2, pp.219-224, 1996.
DOI : 10.1016/0022-328X(95)05914-B

R. A. Benkeser and J. L. Bach, Factors Governing Orientation in Metalation Reactions. III. The Metalation of Alkylferrocenes, Concerning the metallation of alkylferrocenes, pp.890-895, 1964.
DOI : 10.1021/ja01059a029

P. R. Jones and P. Desio, The less familiar reactions of organocadmium reagents, Chemical Reviews, vol.78, issue.5, pp.491-516, 1978.
DOI : 10.1021/cr60315a001

A. F. Shepard, THE SIMPLE HALOGEN DERIVATIVES OF FURAN, Journal of the American Chemical Society, vol.52, issue.5, pp.2083-2090, 1930.
DOI : 10.1021/ja01368a057

E. Negishi, T. Takahashi, S. Baba, D. E. Van-horn, and N. Okukado, Nickel- or palladium-catalyzed cross coupling. 31. Palladium- or nickel-catalyzed reactions of alkenylmetals with unsaturated organic halides as a selective route to arylated alkenes and conjugated dienes: scope, limitations, and mechanism, Journal of the American Chemical Society, vol.109, issue.8, pp.2393-2401, 1987.
DOI : 10.1021/ja00242a024

. K. Org and R. Farrell, See also: (c) Miller, J. A, vol.23, pp.1345-1353, 1987.

C. Amatore, E. Carré, A. Jutand, and M. A. Barki, Rates and Mechanism of the Formation of Zerovalent Palladium Complexes from Mixtures of Pd(OAc)2 and Tertiary Phosphines and Their Reactivity in Oxidative Additions, Organometallics, vol.14, issue.4, pp.1818-1826, 1995.
DOI : 10.1021/om00004a039

M. J. Frisch, Gaussian 03, revision E.01, Phys. Rev. J. Chem. Phys. J. Chem. Phys. Phys. Rev, vol.84, issue.98, pp.3098-3100, 1988.

A. Schäfer, H. Horn, and R. Ahlrichs, Fully optimized contracted Gaussian basis sets for atoms Li to Kr, The Journal of Chemical Physics, vol.97, issue.4, pp.2571-2577, 1992.
DOI : 10.1063/1.463096