01111nas a2200169   4500008004100000245006400041210006300105260000800168300001400176490000800190520054700198100002600745700001800771700003100789700002500820856009600845       2017                        eng d00aNickel-catalyzed direct synthesis of dialkoxymethane ethers0 aNickelcatalyzed direct synthesis of dialkoxymethane ethers  cAUG  a1153-11590 v1293 aA simple and efficient method for the preparation of dialkoxymethane ethers (oxymethylene ethers) from alcohols and paraformaldehyde in the presence of commercially available nickel(II) salt is described. The reaction proceeds readily under neutral, solvent-free conditions using paraformaldehyde as a C-1 source. The present strategy has a broad substrate scope including aliphatic (both primary and secondary) and aromatic alcohols and provides a benign method for the preparation of symmetrical dialkoxymethanes in good yields (up to 89%).1 aSubaramanian, Murugan1 aBera, Abhijit1 aPrasad, Bhagavatula, L. V.1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/nickel-catalyzed-direct-synthesis-dialkoxymethane-ethers01378nas 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<p><span style="color: rgb(51, 51, 51); font-family: arial, helvetica, sans-serif; font-size: 13px; background-color: rgb(248, 248, 248);">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.</span></p>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-activation01207nas 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<p>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.</p>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-co201028nas a2200181   4500008004100000022001400041245008300055210006900138260000800207300001400215490000700229520040800236100001800644700002600662700003000688700002400718856010400742       2018                        eng d  a1523-706000aManganese-catalyzed direct conversion of ester to amide with liberation of H 20 aManganesecatalyzed direct conversion of ester to amide with libe  cJUN  a3381-33840 v203 a<p>A simple and efficient Mn-catalyzed acylation of amines is achieved using both acyl and alkoxy functions of unactivated esters with the liberation of molecular hydrogen as a sole byproduct. The present protocol provides an atom-economical and sustainable route for the synthesis of amides from esters by employing an earth-abundant manganese salt and inexpensive phosphine-free tridentate ligand.</p>1 aMondal, Akash1 aSubaramanian, Murugan1 aAvanashiappan, Nandakumar1 aBalaraman, Kambaram  uhttps://library.ncl.res.in/content/manganese-catalyzed-direct-conversion-ester-amide-liberation-h-201184nas 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-n01174nas a2200205   4500008004100000022001400041245010200055210006900157260000800226300001200234490000600246520045100252100002200703700002700725700002000752700002600772700001900798700002500817856012600842       2018                        eng d  a2044-475300aPhosphine-free cobalt pincer complex catalyzed Z-selective semi-hydrogenation of unbiased alkynes0 aPhosphinefree cobalt pincer complex catalyzed Zselective semihyd  cJAN  a428-4330 v83 a<p>Herein, we report a novel, molecularly defined NNN-type cobalt pincer complex catalyzed transfer semi-hydrogenation of unbiased alkynes to Z-selective alkenes. This unified process is highly stereo-and chemo-selective and exhibits a broad scope as well as wide functional group tolerance. Ammonia-borane (AB), a bench-stable substrate with high gravimetric hydrogen capacity, was used as a safe and practical transfer hydrogenating source.</p>1 aLandge, Vinod, G.1 aPitchaimani, Jayaraman1 aMidya, Siba, P.1 aSubaramanian, Murugan1 aMadhu, Vedichi1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/phosphine-free-cobalt-pincer-complex-catalyzed-z-selective-semi-hydrogenation-unbiased00865nas a2200193   4500008004100000022001400041245010400055210006900159260000900228300001400237490000700251520018500258100002200443700001800465700002600483700002000509700002500529856011700554       2019                        eng d  a1359-734500aNickel(ii)-catalyzed direct olefination of benzyl alcohols with sulfones with the liberation of H-20 aNickeliicatalyzed direct olefination of benzyl alcohols with sul  cMAY   a6130-61330 v553 a<p>A nickel(II)-catalyzed direct olefination of benzyl alcohols with sulfones to access various terminal and internal olefins with the liberation of hydrogen gas is reported.</p>
1 aLandge, Vinod, G.1 aYadav, Vinita1 aSubaramanian, Murugan1 aDangarh, Pragya1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/nickelii-catalyzed-direct-olefination-benzyl-alcohols-sulfones-liberation-h-201362nas a2200169   4500008004100000245010900041210006900150260000800219300001400227490000700241520072800248100002000976700002600996700002101022700002501043856012401068       2019                        eng d00aReusable cobalt catalyst for reversible acceptorless dehydrogenation and hydrogenation of N-Heterocycles0 aReusable cobalt catalyst for reversible acceptorless dehydrogena  cMAY  a2449-24570 v113 a<p><span style="color: rgb(42, 45, 53); font-family: &quot;Source Sans Pro&quot;, Arial, Helvetica, sans-serif; font-size: 14px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(248, 248, 248);">The development of robust catalytic systems based on basemetals for reversible acceptorless dehydrogenation (ADH) and hydrogenation of feedstock chemicals is very important in the context of ` hydrogen storage'. Herein, we report a highly efficient reusable cobalt-based heterogeneous catalyst for reversible dehydrogenation and hydrogenation of N-heterocycles. Both the ADH and the hydrogenation processes operate under mild, benign conditions.</span></p>
1 aJaiswal, Garima1 aSubaramanian, Murugan1 aSahoo, Manoj, K.1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/reusable-cobalt-catalyst-reversible-acceptorless-dehydrogenation-and-hydrogenation-n01330nas a2200205   4500008004100000022001400041245006100055210005900116260000900175300001400184490000700198520069300205100002200898700001700920700001800937700002600955700002500981700002501006856009301031       2020                        eng d  a0022-326300aIron-catalyzed direct julia-type olefination of alcohols0 aIroncatalyzed direct juliatype olefination of alcohols  cAUG   a9876-98860 v853 a<p>Herein, we report an iron-catalyzed, convenient, and expedient strategy for the synthesis of styrene and naphthalene derivatives with the liberation of dihydrogen. The use of a catalyst derived from an earth-abundant metal provides a sustainable strategy to olefins. This method exhibits wide substrate scope (primary and secondary alcohols) functional group tolerance amino, nitro, halo, alkoxy, thiomethoxy, and S- and N-heterocyclic compounds) that can be scaled up. The unprecedented synthesis of 1-methyl naphthalenes proceeds via tandem methenylation/double dehydrogenation. Mechanistic study shows that the cleavage of the C-H bond of alcohol is the rate-determining step.</p>
1 aLandge, Vinod, G.1 aBabu, Reshma1 aYadav, Vinita1 aSubaramanian, Murugan1 aGupta, Virendrakumar1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/iron-catalyzed-direct-julia-type-olefination-alcohols01530nas a2200241   4500008004100000022001400041245007800055210006900133260000800202300001200210490000700222520076900229653003300998653001201031653002201043653001301065653001401078100001801092700002201110700002601132700002501158856010501183       2020                        eng d  a2155-543500aManganese-catalyzed alpha-olefination of nitriles with secondary alcohols0 aManganesecatalyzed alphaolefination of nitriles with secondary a  cJAN  a947-9540 v103 a<p>An expedient catalytic approach for alpha-olefination of nitriles using secondary alcohols with the liberation of molecular hydrogen and water as the only byproducts is reported. This reaction is catalyzed by a molecularly defined manganese(I) pincer complex and operates in the absence of any hydrogen acceptors. A broad range of substrates including cyclic, acyclic, and benzylic alcohols, as well as various nitrile derivatives, such as arylmethyl and heteroarylmethyl nitriles, are employed in the reaction to provide a diverse range of alpha-vinyl nitriles in good to excellent yields. Mechanistic studies showed that the reaction proceeds via dehydrogenative pathway and the activation of alpha(C-H) bond of the alcohol is the rate-determining step.</p>
10aacceptorless dehydrogenation10aAlcohol10aalpha-olefination10aHydrogen10amanganese1 aYadav, Vinita1 aLandge, Vinod, G.1 aSubaramanian, Murugan1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/manganese-catalyzed-alpha-olefination-nitriles-secondary-alcohols02146nas a2200289   4500008004100000022001400041245013400055210006900189260000900258300001200267490000700279520117400286653000801460653001101468653003001479653002301509653002801532100001501560700001901575700002101594700002601615700002501641700002701666700001701693700002301710856012301733       2021                        eng d  a1867-388000aInsights into the nature of self-extinguishing external donors for ziegler-natta catalysis: a combined experimental and DFT study0 aInsights into the nature of selfextinguishing external donors fo  cJAN   a674-6810 v133 a<p>Developing donors for Ziegler-Natta (ZN) catalysis to control the polymerization reaction and produce polymers with desirable properties has always been challenging due to the multi-component nature of the catalytic systems. Here, we have developed a new synthetic protocol for making two external donors, D-1 (2,2,2-trifluoroethyl myristate) and D-2 (2,2,2-trifluoroethyl palmitate) that show self-extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D-1 and D-2 can undergo parallel reactions with aluminum and titanium species present in the system to produce ketones and aldehydes, which are poisons for ZN catalytic systems, thus explaining their self-extinguishing nature. The non-covalent interaction between the long alkyl chain of the donors with the surface plays a vital role in determining the donors ` self-extinguishing nature. There is a significant thermodynamic preference for the binding of the donor with the longer alkyl chain at the titanium center. The current work, therefore, provides interesting insights into how self-extinguishing donors function in ZN catalytic systems.</p>
10aDFT10adonors10anon-covalent interactions10aself-extinguishing10aZiegler-Natta catalysis1 aRaj, Vipin1 aKumawat, Jugal1 aDhamaniya, Sunil1 aSubaramanian, Murugan1 aBalaraman, Ekambaram1 aGupta, Virendra, Kumar1 aVanka, Kumar1 aGrubbs, Robert, H.  uhttps://library.ncl.res.in/content/insights-nature-self-extinguishing-external-donors-ziegler-natta-catalysis-combined01432nas a2200193   4500008004100000022001400041245008400055210006900139260000800208300001400216490000700230520077600237100002001013700002601033700001701059700001801076700002501094856011901119       2021                        eng d  a0022-326300aTandem acceptorless dehydrogenative coupling-decyanation under nickel catalysis0 aTandem acceptorless dehydrogenative couplingdecyanation under ni  cJUN  a7552-75620 v863 aThe development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.1 aMidya, Siba, P.1 aSubaramanian, Murugan1 aBabu, Reshma1 aYadav, Vinita1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/tandem-acceptorless-dehydrogenative-coupling-decyanation-under-nickel-catalysis02102nas a2200289   4500008004100000022001400041245013100055210006900186260000800255300001400263490000700277520110200284653001301386653003201399653002901431653002101460653002101481653001901502100002601521700002301547700002501570700002301595700002501618700001701643700002501660856012701685       2024                        eng d  a2155-543500aDehydrogenative coupling of alcohols with internal alkynes under nickel catalysis: an access to β-deuterated branched ketones0 aDehydrogenative coupling of alcohols with internal alkynes under  cMAY  a8294-83090 v143 a<p>
	In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C-C and C-N bond-forming reactions via the dehydrogenative borrowing hydrogen strategy in traditional transition metal catalysis; however, as an acylating agent in the C-C bond-forming reactions is challenging and rarely reported. Here, we report the dehydrogenative coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol is used as an acylating agent. This reaction system affords a wide range of alpha-branched aryl ketone derivatives with zero waste generation through the umpolung borrowing hydrogen strategy. Moreover, we have demonstrated the chemodivergent applications of the alpha-disubstituted ketones to other valuable building blocks, including large-scale synthesis of beta-deuterated branched ketones. Several spectroscopic studies, intermediate identification, and density functional theory calculations were performed to elucidate the reaction mechanism.</p>
10aAlcohols10aalpha-branched aryl ketones10adehydrogenative coupling10ainternal alkynes10anickel catalysis10apseudoumpolung1 aSubaramanian, Murugan1 aGouda, Chandrakant1 aRoy, Triptesh, Kumar1 aGanesan, Sivakumar1 aBanerjee, Subhrashis1 aVanka, Kumar1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/dehydrogenative-coupling-alcohols-internal-alkynes-under-nickel-catalysis-access-%CE%B201989nas a2200205   4500008004100000022001400041245017100055210006900226260000800295300001400303490000700317520119400324100002601518700002801544700002401572700001501596700001701611700002501628856013001653       2024                        eng d  a2044-475300aNickel-catalyzed tandem conversion of paraformaldehyde : methanol to hydrogen and formate/chemo- and stereoselective hydrogenation of alkynes under neutral conditions0 aNickelcatalyzed tandem conversion of paraformaldehyde methanol t  cMAY  a2779-27930 v143 a<p>
	The development of new catalytic protocols for clean and COx-free hydrogen generation from fundamental feedstocks is always interesting and challenging. Herein, we disclose nickel-catalyzed dihydrogen generation from a mixture of paraformaldehyde-methanol under base-free and activator-free conditions. The dihydrogen generation from this redox combination under neutral, oxidative coupling conditions has been integrated with the hydrogen transfer reactions such as chemo- and stereoselective hydrogenation of alkynes in a tandem manner. This unprecedented strategy provides diverse highly stereoselective olefins with excellent tolerance of reducible functional groups such as ether, silyl ether, aldehyde, keto, ester, nitrile, halides including bromo and iodo groups, and heteroarenes. Additionally, we demonstrated catalytic stereo-interconversion of alkenes under benign conditions. The affordable gram-scale synthesis of some important pharmaceutical bioactive molecules has further enhanced their synthetic value. A tandem dihydrogen generation from a mixture of paraformaldehyde-methanol under base-free conditions followed by semihydrogenation of alkynes is reported.</p>
1 aSubaramanian, Murugan1 aPadhy, Subarna, Sukanya1 aGouda, Chandrakanth1 aDas, Tamal1 aVanka, Kumar1 aBalaraman, Ekambaram  uhttps://library.ncl.res.in/content/nickel-catalyzed-tandem-conversion-paraformaldehyde-methanol-hydrogen-and-formatechemo-and