01330nas a2200193 4500008004100000245008000041210007100121260000800192300001400200490000700214520048400221653019300705100003000898700002400928700002000952700002300972700002500995856011601020 2016 eng d00aExpedient cobalt-catalyzed C–H alkynylation of (enantiopure) benzylamines0 aExpedient cobaltcatalyzed C–H alkynylation of enantiopure benzyl cOCT a5252-52550 v183 a

A unified strategy for cobalt-catalyzed ortho-C-H bond alkynylation of benzylamines is reported. Simple, commercially available CoBr2 was used as a cobalt source. The developed alkynylation strategy is robust and efficient and has a broad substrate scope including 1 degrees, 2 degrees, and 3 degrees benzylamines. The mechanistic study shows that C-H bond cleavage is reversible, and the kinetic study illustrates that the rate of reaction depends solely on the catalyst.

10aTerminal Alkynes; Bond Activation; Directed Functionalization;Aminoquinoline Benzamides; Ortho-C(Sp(2))-H Bonds; Mechanistic Insights; Selective Access; Carbon-Hydrogen; Nickel; Annulation1 aLandge, Vinod, Gokulkrish1 aMidya, Siba, Prasad1 aRana, Jagannath1 aShinde, Dinesh, R.1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/expedient-cobalt-catalyzed-c%E2%80%93h-alkynylation-enantiopure-benzylamines01060nas a2200181 4500008004100000245010800041210006900149260000800218300001400226490000700240520039500247100002000642700002000662700002000682700002100702700002500723856013000748 2017 eng d00aMetal-free radical trifluoromethylation of beta-nitroalkenes through visible-light photoredox catalysis0 aMetalfree radical trifluoromethylation of betanitroalkenes throu cJUN a6760-67630 v533 aA catalytic method for functional group interconversion is immensely important in modern sciences. Here, we report an efficient catalytic conversion of nitroalkenes to highly stereoselective 1-trifluoromethylalkenes at room temperature. This unprecedented metal-free photocatalytic strategy is simple and operates under visible-light irradiation using the commercially available CF3 source.1 aMidya, Siba, P.1 aRana, Jagannath1 aAbraham, Thomas1 aAswin, Bhaskaran1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/metal-free-radical-trifluoromethylation-beta-nitroalkenes-through-visible-light-photoredox01378nas a2200301 4500008004100000022001400041245008300055210006900138260000800207300001500215490000700230520045900237653001500696653002400711653001300735653002000748653001200768653001800780653001200798653001600810653001600826653003000842100002200872700002000894700002600914700002500940856011100965 2017 eng d a1477-052000aNickel-catalyzed N-vinylation of heteroaromatic amines via C-H bond activation0 aNickelcatalyzed Nvinylation of heteroaromatic amines via CH bond cSEP a 6896-69000 v153 a

Here, we report a ligand- and reductant-free nickel-catalyzed N-vinylation of heteroaromatic amines using biorenewable p-cymene as a solvent. This unprecedented cross-coupling strategy has high functional group tolerance (halides, alkoxy, cyano, chiral motif, etc.) and proceeded via C-H bond activation.

10aAlkylation10aAmination Reactions10aAnilines10aAryl Chlorides10ahalides10aMonoarylation10aO Bonds10aPrecatalyst10aPyrimidines10aRemoveble Directing Group1 aLandge, Vinod, G.1 aRana, Jagannath1 aSubaramanian, Murugan1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/nickel-catalyzed-n-vinylation-heteroaromatic-amines-c-h-bond-activation01063nas a2200169 4500008004100000245007600041210006900117260000800186300001600194490000700210520048200217100002100699700002000720700002000740700002500760856010800785 2017 eng d00aOrgano-photoredox catalyzed oxidative dehydrogenation of N-heterocycles0 aOrganophotoredox catalyzed oxidative dehydrogenation of Nheteroc cOCT a14167-141720 v233 aWe report here for the first time the catalytic oxidative dehydrogenation of N-heterocycles by a visible-light organo-photoredox catalyst with low catalyst loading (0.1-1mol%). The reaction proceeds efficiently under base- and additive-free conditions with ambient air at room temperature. The utility of this benign approach is demonstrated by the synthesis of various pharmaceutically relevant N-heteroarenes such as quinoline, quinoxaline, quinazoline, acridine, and indole.1 aSahoo, Manoj, K.1 aJaiswal, Garima1 aRana, Jagannath1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/organo-photoredox-catalyzed-oxidative-dehydrogenation-n-heterocycles01207nas a2200169 4500008004100000245015300041210006900194260000800263300001400271490000600285520052300291100002100814700002000835700002600855700002500881856013100906 2017 eng d00aRoom-temperature direct arylation of anilides under external oxidant-free conditions using CO2-Derived Dimethyl Carbonate (DMC) as a 'green' solvent0 aRoomtemperature direct arylation of anilides under external oxid cAUG a7565-75690 v23 a

Here, an efficient catalytic protocol for direct C-H bond arylation of anilides under base- and external oxidant-free conditions is reported. This reaction proceeds readily at room temperature using CO2-derived dimethyl carbonate (DMC) as a green solvent under visible-light dual catalysis. Later, application of our strategy for the gram-scale synthesis of Boscalid has been successfully shown. An unprecedented unsymmetrical bis-arylation of anilides is also demonstrated under mild, redox-neutral conditions.

1 aSahoo, Manoj, K.1 aRana, Jagannath1 aSubaramanian, Murugan1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/room-temperature-direct-arylation-anilides-under-external-oxidant-free-conditions-using-co200985nas a2200193 4500008004100000022001400041245015100055210006900206260000800275300001000283490000700293520025200300100002000552700002200572700002100594700002000615700002500635856013100660 2018 eng d a1359-734500aCobalt-catalyzed acceptorless dehydrogenative coupling of aminoalcohols with alcohols: direct access to pyrrole, pyridine and pyrazine derivatives0 aCobaltcatalyzed acceptorless dehydrogenative coupling of aminoal cJAN a90-930 v543 a

Here, the first example is reported of a new, molecularly defined SNS-cobalt(II) catalyst for the acceptorless dehydrogenative coupling (ADC) of unprotected amino alcohols with secondary alcohols leading to pyrrole and pyridine derivatives.

1 aMidya, Siba, P.1 aLandge, Vinod, G.1 aSahoo, Manoj, K.1 aRana, Jagannath1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/cobalt-catalyzed-acceptorless-dehydrogenative-coupling-aminoalcohols-alcohols-direct-access01486nas a2200193 4500008004100000245011800041210006900159260000800228300001400236490000700250520076300257100002001020700002001040700002701060700003001087700001901117700002501136856013101161 2018 eng d00a Ni-catalyzed alpha-alkylation of unactivated amides and esters with alcohols by hydrogen auto-transfer strategy 0 aNicatalyzed alphaalkylation of unactivated amides and esters wit cNOV a3911-39160 v113 aA transition-metal-catalyzed borrowing hydrogen/hydrogen auto-transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C-N and C-C bonds. In this study, a nickel-catalyzed alpha-alkylation of unactivated amides and ester (tert-butyl acetate) is carried out by using primary alcohols under mild conditions. This C-C bond-forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN-pincer complex (0.1-1 mol %) and proceeds through hydrogen auto-transfer, thereby releasing water as the sole byproduct. In addition, N-alkylation of cyclic amides under Ni-catalytic conditions is demonstrated.1 aMidya, Siba, P.1 aRana, Jagannath1 aPitchaimani, Jayaraman1 aNandakumar, Avanashiappan1 aMadhu, Vedichi1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/ni-catalyzed-alpha-alkylation-unactivated-amides-and-esters-alcohols-hydrogen-auto-transfer01184nas a2200169 4500008004100000245010600041210006900147260000800216300001400224490000600238520056500244100002000809700001700829700002600846700002500872856011700897 2018 eng d00aNi-catalyzed dehydrogenative coupling of primary and secondary alcohols with methyl-N-heteroaromatics0 aNicatalyzed dehydrogenative coupling of primary and secondary al cNOV a3250-32550 v53 aHere we report the first base-metal catalyzed dehydrogenative coupling of primary (aromatic, heteroaromatic, and aliphatic) and secondary alcohols with methyl-N-heteroaromatics to form various C(sp(3))-alkylated N-heteroaromatics. The reaction is enabled by Earth abundant, non-precious NiBr2 as a transition metal catalyst and N,N,N,N-tetramethylethylenediamine (TMEDA) as a ligand system. Mechanistic studies reveal that a hydrogen auto-transfer process is involved in the direct C(sp(3))-alkylation and the reaction proceeds through an -olefination process.1 aRana, Jagannath1 aBabu, Reshma1 aSubaramanian, Murugan1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/ni-catalyzed-dehydrogenative-coupling-primary-and-secondary-alcohols-methyl-n00982nas a2200169 4500008004100000022001400041245011900055210006900174260000900243300001400252490000700266520034400273100002000617700002500637700002500662856012500687 2019 eng d a1477-922600aManganese-catalyzed direct C-C coupling of -C-H bonds of amides and esters with alcohols via hydrogen autotransfer0 aManganesecatalyzed direct CC coupling of CH bonds of amides and  cJUN  a7094-70990 v483 a

Herein we report an efficient manganese-catalyzed C-alkylation of unactivated amides and tert-butyl acetate using alcohols as alkylating agents. This elegant approach exhibits a broad substrate scope providing the C-C coupled products of amides via a hydrogen auto-transfer strategy using aryl, heteroaryl, and aliphatic alcohols.

1 aRana, Jagannath1 aGupta, Virendrakumar1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/manganese-catalyzed-direct-c-c-coupling-c-h-bonds-amides-and-esters-alcohols-hydrogen