00865nas 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

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.

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-201330nas 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

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.

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

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.

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-alcohols01315nas a2200229 4500008004100000022001400041245011300055210006900168260000900237300001400246490000800260520053100268653003300799653001200832653001100844653001400855653001900869100001800888700002500906700002400931856013000955 2021 eng d a1615-415000aPhosphine-free manganese(II)-catalyst enables acceptorless dehydrogenative coupling of alcohols with indoles0 aPhosphinefree manganeseIIcatalyst enables acceptorless dehydroge cSEP  a4430-44390 v3633 aHerein, an air-stable, molecularly defined NNN-Mn(II) pincer complex catalyzed acceptorless dehydrogenative coupling of alcohols with indoles is reported. A wide variety of symmetrical and unsymmetrical bis(indolyl)methane derivatives as well as some structurally important products such as Vibrindole A, Turbomycin B alkaloid, Antileukemic, and Anticancer agents were synthesized. Mechanistic studies illustrate the importance of the NH moiety in the complex and the crucial role of metal-ligand cooperation during catalysis.10aacceptorless dehydrogenation10aAlcohol10aIndole10amanganese10aphosphine-free1 aYadav, Vinita1 aBalaraman, Ekambaram1 aMhaske, Santosh, B. uhttps://library.ncl.res.in/content/phosphine-free-manganeseii-catalyst-enables-acceptorless-dehydrogenative-coupling-alcohols02732nas a2200169 4500008004100000245009100041210006900132260000800201300001600209490000700225520219400232100001802426700002302444700002502467700002502492856004502517 2021 eng d00aRecent advances in liquid organic hydrogen carriers: an alcohol-based hydrogen economy0 aRecent advances in liquid organic hydrogen carriers an alcoholba cNOV a14712-147260 v113 aEnergy storage and the use of abundantly available feedstock without contributing to the carbon footprint are two significant global challenges. In this regard, the development of high-performance, low-cost, sustainable, and environmentally friendly energy storage and production systems is crucial to fulfill the growing energy demands of the current society. The use of hydrogen will diversify energy sources as it significantly reduces greenhouse gas emissions and environmental pollution during energy conversion. Although the hydrogen economy is quite beneficial, hydrogen storage is still very challenging, and the existing methods suffer from a lot of problems and drawbacks. The conventional liquefaction and compression hydrogen storage technologies are associated with several challenges, including low storage density, boil-off losses, relatively high costs, and safety and transportation concerns. In recent years, liquid organic hydrogen carrier (LOHC) systems have attained a lot of importance as a substitute for the traditional storage methods. Hydrogen storage and transport using LOHCs are based on two-step cycles, such as (i) loading/storage of hydrogen by catalytic hydrogenation of H2-lean compounds and (ii) unloading/releasing hydrogen by dehydrogenating the resulting H2-rich liquids. Since alcohols are widely accessible from various industrial processes or even from biomass-derived precursors, the catalytic acceptorless dehydrogenation of alcohols is an attractive approach for future hydrogen storage applications. Hence, the catalytic dehydrogenation-hydrogenation of alcohols can be used for the development of alcohol-based LOHC systems which are economical, safe, and easy to handle. Further, they are similar to crude oils under ambient conditions and thus are suitable for use in the current energy infrastructure. This Review covers several essential aspects of these developing efficient and abundantly available LOHC systems for efficient hydrogen storage and transport applications. Additionally, reversible LOHC systems based on the catalytic dehydrogenation-hydrogenation of alcohols and their corresponding carbonyl compounds have been discussed.1 aYadav, Vinita1 aSivakumar, Ganesan1 aGupta, Virendrakumar1 aBalaraman, Ekambaram uhttps://doi.org/10.1021/acscatal.1c0328301850nas a2200205 4500008004100000022001400041245011800055210006900173260000800242300001400250490000700264520113500271100001701406700002401423700001901447700001801466700001901484700001701503856012401520 2021 eng d a0276-733300aSubstrate, catalyst, and solvent: the triune nature of multitasking reagents in hydroboration and cyanosilylation0 aSubstrate catalyst and solvent the triune nature of multitasking cAPR a1104-11120 v403 a

A truly green chemical process would avoid the use of an external catalyst, while still achieving high efficiency. This has been realized in the very recent past for hydroboration, cyanosilylation, acetalization, and the aza-Michael addition, among other reactions. The current combined computational and experimental study unlocks the secret to how this highly desirable outcome is accomplished: one of the reactants in the process also acts as the catalyst. Specifically, this is shown (i) for the important hydroboration reaction, with pinacolborane (HBpin) as the hydroborating reagent and benzaldehyde, acetophenone, benzoic acid and p-methoxyphenylacetylene as the hydroborated substrates, and (ii) for cyanosilylation, with trimethylcyanosilane (TMSCN) as the cyanosilylating agent and benzaldehyde as the substrate. The mechanistic understanding thus gained has then been further exploited experimentally to bring hydroboration and cyanosilylation closer to experimental conditions in catalysis. These insights can potentially be expanded to the rapidly growing area of solvent-free and internal catalyst chemistry.

1 aDixit, Ruchi1 aBisai, Milan, Kumar1 aYadav, Sandeep1 aYadav, Vinita1 aSen, Sakya, S.1 aVanka, Kumar uhttps://library.ncl.res.in/content/substrate-catalyst-and-solvent-triune-nature-multitasking-reagents-hydroboration-and01432nas 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-catalysis01505nas a2200181 4500008004100000022001400041245009600055210006900151260000800220300001400228490000700242520086100249100001801110700002301128700002501151700002401176856012301200 2022 eng d a1523-706000aNickel-catalyzed direct synthesis of N-substituted indoles from amino alcohols and alcohols0 aNickelcatalyzed direct synthesis of Nsubstituted indoles from am cDEC a9054-90590 v243 a

A one-pot cascade approach for the synthesis of N substituted indoles from amino alcohols and alcohols under additive and base-free conditions with the liberation of water as the only stoichiometric byproduct is reported. The commercially available bench-stable Ni(OTf)2 salt in combination with 1,2-bis(dicyclohexylphosphino)ethane (dcype) is very effective for this unprecedented catalytic transformation. A broad range of substrates including aromatic and aliphatic primary alcohols, cyclic and acyclic secondary alcohols, and various substituted 2-aminophenyl ethyl alcohols are employed in the reaction conditions to provide a diverse range of N-alkylated indoles. Mechanistic studies revealed that the reaction proceeds through tandem N-alkylation via hydrogen autotransfer followed by the cyclization of N-alkylated alcohol intermediate.

1 aYadav, Vinita1 aJagtap, Sayali, G.1 aBalaraman, Ekambaram1 aMhaske, Santosh, B. uhttps://library.ncl.res.in/content/nickel-catalyzed-direct-synthesis-n-substituted-indoles-amino-alcohols-and-alcohols01198nas a2200181 4500008004100000022001400041245013600055210006900191260000900260300001600269490000700285520051500292100002300807700001800830700002400848700002400872856012000896 2024 eng d a0022-326300aRegio- and stereoselective construction of 1,3,5-triaroylcyclohexanes via KO t Bu-mediated cyclotrimerization of aryl vinyl ketones0 aRegio and stereoselective construction of 135triaroylcyclohexane cNOV  a17207-172120 v893 a

Herein, we disclose a simple one-pot method for an efficient regio- and stereoselective synthesis of 1,3,5-triaroylcyclohexanes from aryl vinyl ketones using potassium tert-butoxide. The developed protocol allows the construction of various symmetrically substituted cyclohexanes in good to excellent yields. The major product 2 also can be converted to the product 3 (all equatorial) conveniently by acid catalysis. This protocol features a good substrate scope and functional group compatibility.

1 aMahale, Sachin, D.1 aYadav, Vinita1 aGonnade, Rajesh, G.1 aMhaske, Santosh, B. uhttps://library.ncl.res.in/content/regio-and-stereoselective-construction-135-triaroylcyclohexanes-ko-t-bu-mediated