@article {42739,
	title = {Mechanistic insights into pincer-ligated palladium-catalyzed arylation of azoles with aryl Iodides: evidence of a Pd-II-Pd-IV-Pd-II pathway},
	journal = {Organometallics},
	volume = {35},
	year = {2016},
	month = {MAR},
	pages = {875{\textendash}886},
	abstract = {<p>Pincer-based (R2POCNR'2)PdCl complexes along with CuI cocatalyst catalyze the arylation of azoles with aryl iodides to give the 2-arylated azole products. Herein, we report an extensive mechanistic investigation for the direct arylation of azoles involving a well-defined and highly efficient (iPr2POCNEt2)PdCl (2a) catalyst, which emphasizes a rare PdII{\textendash}PdIV{\textendash}PdII redox catalytic pathway. Kinetic studies and deuterium labeling experiments indicate that the C{\textendash}H bond cleavage on azoles occurs via two distinct routes in a reversible manner. Controlled reactivity of the catalyst 2a underlines the iodo derivative (iPr2POCNEt2)PdI (3a) to be the resting state of the catalyst. The intermediate species (iPr2POCNEt2)Pd-benzothiazolyl (4a) has been isolated and structurally characterized. A determination of reaction rates of compound 4a with electronically different aryl iodides has revealed the kinetic significance of the oxidative addition of the C(sp2){\textendash}X electrophile, aryl iodide, to complex 4a. Furthermore, the reactivity behavior of 4a suggests that the arylation of benzothiazole proceeds via an oxidative addition/reductive elimination pathway involving a (iPr2POCNEt2)PdIV(benzothiazolyl)(Ar)I species, which is strongly supported by DFT calculations.</p>},
	doi = {10.1021/acs.organomet.6b00003},
	author = {Khake, Shrikant M. and Jagtap, Rahul A. and Dangat, Yuvraj B. and Gonnade, Rajesh G. and Vanka, Kumar and Punji, Benudhar}
}
@article {46818,
	title = {MnBr2-catalyzed direct and site-selective alkylation of indoles and benzo[h]quinoline},
	journal = {Organic Letters},
	volume = {22},
	year = {2020},
	month = {JUN},
	pages = {4643-4647},
	type = {Article},
	abstract = {<p>Manganese-catalyzed regioselective C-H alkylation of indoles and benzo[h]quinoline with a variety of unactivated alkyl iodides is reported. Unlike other Mn-catalyzed C-H functionalization, this protocol does not require a Grignard reagent base and employs a simple and inexpensive MnBr2 as a catalyst. This method tolerates diverse functionalities, including fluoro, chloro, bromo, iodo, alkenyl, alkynyl, pyrrolyl, and carbazolyl groups. The alkylation proceeds through a single-electron transfer pathway comprising reversible C-H manganesation and involving an alkyl radical intermediate.</p>
},
	issn = {1523-7060},
	doi = {10.1021/acs.orglett.0c01398},
	author = {Jagtap, Rahul A. and Verma, Suryadev K. and Punji, Benudhar}
}
