01344nas a2200157   4500008004100000022001400041245010400055210006900159260000900228300001400237490000700251520076000258100002601018700002001044856012201064       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  uhttp://library.ncl.res.in/content/pdii-catalyzed-chemoselective-acetoxylation-csp2-h-and-csp3-h-bonds-tertiary-amides01288nas a2200181   4500008004100000022001400041245009300055210006900148260000800217300001400225490000700239520065100246100002600897700002200923700002400945700002000969856011700989       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  uhttp://library.ncl.res.in/content/palladium-catalyzed-chemoselective-oxygenation-csp2-h-and-csp3-h-bonds-isatins02020nas a2200217   4500008004100000022001400041245011000055210006900165260000800234490000700242520126500249653001901514653001201533653001401545653001901559653002601578100002601604700002401630700002001654856012801674       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  uhttp://library.ncl.res.in/content/palladium-catalyzed-regioselective-c4-h-fluoroalkoxylation-indoles-through-weak-chelation