01506nas a2200145   4500008004100000022002200041245009200063210006900155260002100224300001200245520094700257100001801204700002001222856011801242       2017                        eng d  a978-0-12-805254-900aPalladacycles for directed and nondirected C H bond functionalization of (Hetero)arenes0 aPalladacycles for directed and nondirected C H bond functionaliz  aMumbaibElsevier  a357-4153 aApplication of palladacycle complexes in catalytic organic transformation is rapidly expanding. This chapter is mainly focused on the use of palladacycle precatalysts in CH bond functionalizations, as well as an overview of palladacycle intermediates in directed CH bond functionalization reactions. The described palladacycle precatalysts are more efficient and more selective than the traditional palladium complexes for CH bond functionalization processes. The second part of the chapter summarizes the involvement of palladacycle intermediates in various directed CH bond functionalizations that are proposed with experimental evidence. Some of the palladacycle intermediates described are shown to be competent as catalyst precursors. It has been demonstrated that the formation of palladacycle (precatalyst or intermediate) makes the CH functionalization process more facile, because of the high stability associated with palladacycles.1 aSoni, Vineeta1 aPunji, Benudhar  uhttps://library.ncl.res.in/content/palladacycles-directed-and-nondirected-c-h-bond-functionalization-heteroarenes01345nas a2200157   4500008004100000022001400041245010400055210006900159260000900228300001400237490000700251520076000258100002601018700002001044856012301064       2021                        eng d  a0022-326300aPd(II)-catalyzed chemoselective acetoxylation of C(sp(2))-H and C(sp(3))-H bonds in tertiary amides0 aPdIIcatalyzed chemoselective acetoxylation of Csp2H and Csp3H bo  cJUN   a8172-81810 v863 aPalladium-catalyzed chemoselective C(sp(2))-H and C(sp(3))-H acetoxylation of synthetically useful tertiary amides is reported under relatively mild reaction conditions. This protocol proceeds through the assistance of a weakly coordinated directing group (C = O) and requires low catalyst (1.0 mol %) loading. Diverse functionalities, such as C(sp(2))-Cl, C(sp(3))-Cl, -CF3, -COOEt, and -NO2 groups, including morpholinyl, piperazinyl, and pyrrolidinyl heterocycles, are compatible under the reaction conditions. Further functionalization of this protocol is demonstrated by hydrolysis to alcohols, alcohol-acids, as well as reduction to tertiary amines. A preliminary kinetic isotope effect study supported the rate-limiting C-H bond activation process.1 aVijaykumar, Muniyappa1 aPunji, Benudhar  uhttps://library.ncl.res.in/content/pdii-catalyzed-chemoselective-acetoxylation-csp2-h-and-csp3-h-bonds-tertiary-amides01289nas a2200181   4500008004100000022001400041245009300055210006900148260000800217300001400225490000700239520065100246100002600897700002200923700002400945700002000969856011800989       2023                        eng d  a1523-706000aPalladium-catalyzed chemoselective oxygenation of C(sp2)-H and C(sp3)-H bonds in isatins0 aPalladiumcatalyzed chemoselective oxygenation of Csp2H and Csp3H  cMAR  a1862-18670 v253 a<p>
	The palladium-catalyzed chemoselective C(sp2)-H and C(sp3)-H bond oxygenation of substituted isatin derivatives is reported. This mild protocol exhibits the C5 C(sp2)-H oxygenation of isatins through electrophilic intermolecular C-H palladation in concentrated solutions using PhI(OAc)2 or Selectfluor as an oxidant, whereas it exhibits- N-CH3 C(sp3)-H oxygenation in dilute solutions via carbonyl-assisted intramolecular palladation in the presence of K2S2O8. This oxygenation reaction provides a direct and unified approach for synthesizing diverse oxygenated isatins with sensitive functionalities, including biorelevant compounds.</p>
1 aVijaykumar, Muniyappa1 aPradhan, Chandini1 aGonnade, Rajesh, G.1 aPunji, Benudhar  uhttps://library.ncl.res.in/content/palladium-catalyzed-chemoselective-oxygenation-csp2-h-and-csp3-h-bonds-isatins02021nas a2200217   4500008004100000022001400041245011000055210006900165260000800234490000700242520126500249653001901514653001201533653001401545653001901559653002601578100002601604700002401630700002001654856012901674       2025                        eng d  a1867-388000aPalladium-catalyzed regioselective C(4)-H fluoroalkoxylation of indoles through weak chelation assistance0 aPalladiumcatalyzed regioselective C4H fluoroalkoxylation of indo  cJAN0 v173 a<p>
	Installing fluoroalkyl motifs into biorelevant indoles is particularly interesting due to their ubiquitous presence in drug molecules. Herein, we demonstrate the regioselective C4 fluoroalkoxylation of indoles using fluoroalcohols via palladium-catalyzed chelation-assisted C &amp; horbar;H activation. The weak chelating benzoyl moiety at the C3 position acts as a directing group for remote C(4)&amp; horbar;H fluoroalkoxylation of diversely substituted indoles. This methodology demonstrates a high level of regioselectivity and tolerates a range of crucial functional groups, yielding diverse trifluoroalkoxylated indoles in moderate to good yields. Removal of directing/protecting groups and further functionalization established the synthetic utility of the methodology. A preliminary mechanistic investigation is conducted by isolating the palladacycle intermediate and performing the deuterium scrambling study. The regioselective C4 fluoroalkoxylation of indoles with various fluoroalcohols is achieved by the palladium-catalyzed weak chelation assistance strategy. The reaction is compatible for a range of important functionalities and proceeds via the intermediacy of a six-membered palladacycle following a Pd(II)/Pd(IV) pathway. image</p>
10aC-H activation10aindoles10aPalladium10aRegioselective10aTrifluoroalkoxylation1 aVijaykumar, Muniyappa1 aGonnade, Rajesh, G.1 aPunji, Benudhar  uhttps://library.ncl.res.in/content/palladium-catalyzed-regioselective-c4-h-fluoroalkoxylation-indoles-through-weak-chelation