@article { ISI:000232011300008, title = {Nitrogen ligands: The transition metal catalyzed reaction of aryl halides with olefins (Mizoroki-Heck), phenylboronic acid (Suzuki coupling) and Buchwald-Hartwig amination, new catalysts and effect of co-catalysts - Aryl halide activation - Part I}, journal = {Indian Journal of Chemistry Section B-Organic Chemistry including Medicinal Chemistry}, volume = {44}, number = {9}, year = {2005}, month = {SEP}, pages = {1894-1908}, publisher = {COUNCIL SCIENTIFIC \& INDUSTRIAL RES}, type = {Article}, address = {ANUSANDHAN BHAWAN, 2 RAFI MARG, NEW DELHI, 110001, INDIA}, abstract = {

Nitrogen ligands are an excellent alternative for the traditional P-ligands in the Pd catalyzed Mizoroki-Fleck reaction, Suzuki coupling and Buchwald-Hartwig aryl amination. Pd complexes of dimethyl glyoxime, 8-hydroxyquinoline, salen, picolinic acid, and DAB ligands gave high yields of the E-cinnamates and E-stilbenes from aryl iodides. Acetophenone oxime N, N-dimethybenzylamine and ferrocenyl oxime palladacycle are better catalysts with comparable yields, high TON (95, 000) and TOF{\textquoteright}s (2, 500 h(-1)) to P-ligand catalysts. Aryl bromides and in a few cases, aryl chlorides could also be activated by these complexes by the use of Lewis acid and (C(4)H(9))(4)NI as additives. Cy-DAB ligands gave good yields with electron rich aryl bromides and the use of ionic liquid improve the yield. These N-ligand metal complexes can be readily synthesized and the ligands possess the advantage of easy functional group modifications and convenient synthetic methods compared to P-ligands. The degradation reactions associated with P-ligands are not observed in the N-ligands, with comparable, high thermal, moisture and air stability and insensitivity. Activation of aryl bromides (Mizoroki-Fleck reaction, Suzuki reaction) could be achieved in high yields, TON and TOF (86-94\% yield, TON: 36, 000-90, 000, TOF:6, 000-11, 500 h-1) catalyzed by monomeric amine and oxime palladacycles (Cat-8, 11, 13 B) with a N-heterocyclic carbene ligand better than a phosphorous ligand. Molten (C(4)H(9))(4)NBr is an efficient ionic liquid medium for the Mizoroki-Fleck reaction of aryl bromides, giving higher yields. Low to moderate yields of aryl amination are obtained with the carbene pallaclacycle and N, N-dibenzyl piperazine Pd complexes.

}, keywords = {DAB, DMG, Mizoroki-Heck reaction, nitrogen ligands, Palladacycle}, issn = {0376-4699}, author = {Iyer, S and Kulkarni, GM and Ramesh, C and Sattar, AK} } @article {51}, title = {Organotin-oxometalate coordination polymer catalyzed oxyfunctionalization of monoterpenes}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {270}, number = {1-2}, year = {2007}, month = {JUN}, pages = {177-184}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, keywords = {Heck reaction, kinetics, Palladacycle}, issn = {1381-1169}, doi = {10.1016/j.molcata.2007.01.035}, author = {Bordoloi, Ankur and Lefebvre, F. and Halligudi, Shivaraj B.} } @article { ISI:000268905100015, title = {Kinetics of arylation of 3-bromo-benzophenone with n-butylacrylate using NC palladacycle catalyst}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {309}, number = {1-2}, year = {2009}, month = {AUG}, pages = {111-116}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The kinetics of arylation of n-butylacrylate (n-BA) with 3-bromo-benzophenone (BBP) using a monomeric palladacycle complex [Pd(ppy)(PPh(3))(OTs)](ppy=2-phenylpyridine) catalyst has been studied. The effect of concentration of the substrate, base (NaOAc), and catalyst was studied at three different temperatures (413-433 K). The rate was found to be first order with respect to catalyst, first order tending to zero order with respect to n-butylacrylate and NaOAc concentrations. The rate passed through a maximum with variation of BBP concentration. The observed results have been explained on the basis of formation of Pd species (PdX(2), PdX(3)(-), PdX(4)(2-), and Pd(2)X(6)(2-)) which are inactive for the Heck reaction. Various empirical rate equations were considered to fit the rate data and the best fitting model has been selected. The rates predicted by model were found to be in good agreement with the observed experimental data. (C) 2009 Elsevier B.V. All rights reserved.

}, keywords = {Arylation, Heck reaction, kinetics, Palladacycle}, issn = {1381-1169}, doi = {10.1016/j.molcata.2009.05.003}, author = {Atla, Shashi B. and Rajurkar, Kalpendra B. and Kelkar, Ashutosh A. and Chaudhari, Raghunath V.} } @article { ISI:000263365600013, title = {NC palladacycles in the Heck arylation of ethylene: synthesis, structure and their reactivity}, journal = {Journal of Organometallic Chemistry}, volume = {694}, number = {5}, year = {2009}, month = {MAR}, pages = {683-690}, publisher = {ELSEVIER SCIENCE SA}, address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND}, abstract = {

Monomeric cyclopalladated complexes with NC coordination using ligands 2-phenylpyridine, 2-phenylquinoline, 8-methylquinoline have been synthesized and the structures have been determined by single crystal X-ray structure analysis. The crystal structures of monomeric palladacycles prepared using benzophenone oxime, and 2-phenylpyridine have also been determined. The use of these complexes in the Heck arylation of ethylene with 2-bromo-6-methoxynaphthalne (BMN) to give 2-vinyl-6-methoxynapthalene which is an intermediate for the synthesis of anti-inflammatory drug Naproxen has been examined and also arylation of ethylene with 3-bromo-benzophenone and 4-bromo-isobutylbenzene was investigated. These palladacycles with NC coordination show excellent catalytic activity with a TOF \> 4000 h (1). (C) 2008 Elsevier B.V. All rights reserved.

}, keywords = {alpha-Aryl propionic acids, Arylation, Palladacycle}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2008.11.065}, author = {Atla, Shashi B. and Kelkar, Ashutosh A. and Puranik, Vedavati G. and Bensch, Wolfgang and Chaudhari, Raghunath V.} } @article { ISI:000325204200090, title = {Cinnamic acid derivatives via heck reaction in an aqueous-biphasic catalytic system with easy catalyst-product separation}, journal = {Asian Journal of Chemistry}, volume = {25}, number = {15, A}, year = {2013}, month = {NOV}, pages = {8633-8637}, publisher = {ASIAN JOURNAL OF CHEMISTRY}, address = {11/100 RAJENDRA NAGAR, SECTOR 3,, SAHIBABAD 201 005, GHAZIABAD, INDIA}, abstract = {

A true biphasic [aqueous-organic] system for the coupling of water soluble sodium acrylate with different aryl halides for the synthesis of cinnamic acid derivatives has been developed, employing palladium catalysts that is soluble in organic phase. Amongst them, palladacycle was found to be stable in presence of water and could be recycled for four times with no loss in the activity. Such a system facilitates easy recycle of catalyst and also the removal of the salts from the catalyst phase, ensuring high activity with respect to cumulative turn over number (TON) and turn over frequency (TOF). The reaction was facilitated by organic as well as inorganic bases. The efficiency of the catalyst, role of organic/inorganic bases on the activity is reported.

}, keywords = {Biphasic catalysis, Heck reaction, Palladacycle, Separation}, issn = {0970-7077}, author = {Jagtap, Sangeeta Vijay and Deshpande, R. M.} }