00981nas a2200181 4500008004100000245013100041210006900172260000800241300001600249490000800265520028300273100002200556700002500578700002800603700002400631700002000655856012400675 2012 eng d00aRuthenium pincer-catalyzed cross-dehydrogenative coupling of primary alcohols with secondary alcohols under neutral conditions0 aRuthenium pincercatalyzed crossdehydrogenative coupling of prima cSEP a2403–24060 v3543 a

Cross-dehydrogenative coupling of primary alcohols with secondary alcohols to obtain mixed esters with the liberation of molecular hydrogen is achieved in high yield and good selectivity under neutral conditions, using a bipyridyl-based PNN ruthenium(II) pincer catalyst.

1 aSrimani, Dipankar1 aBalaraman, Ekambaram1 aGnanaprakasam, Boopathy1 aBen-David, Yehoshoa1 aMilstein, David uhttps://library.ncl.res.in/content/ruthenium-pincer-catalyzed-cross-dehydrogenative-coupling-primary-alcohols-secondary01913nas a2200193 4500008004100000022001400041245011000055210006900165260009000234300002500324490000600349520110800355100002401463700002401487700003001511700002401541700002501565856012901590 2015 eng d a2041-172300aReversed reactivity of anilines with alkynes in the rhodium-catalysed C-H activation/carbonylation tandem0 aReversed reactivity of anilines with alkynes in the rhodiumcatal aMACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLANDbNATURE PUBLISHING GROUPcOCT aArticle Number: 85910 v63 a

Development of multicatalytic approach consisting of two or more mechanistically distinct catalytic steps using a single-site catalyst for rapid and straightforward access of structurally complex molecules under eco-benign conditions has significance in contemporary science. We have developed herein a rhodium-catalysed C-H activation strategy which uses an unprotected anilines and an electron-deficient alkynes to C-C bonded products as a potential intermediate in contrast to the archetypical C-N bonded products with high levels of regioselectivity. This is followed by carbonylation of C-H bond activated intermediate and subsequent annulation into quinolines has been described. This rhodium-catalysed auto-tandem reaction operates under mild, environmentally benign conditions using water as the solvent and CO surrogates as the carbonyl source with the concomitant generation of hydrogen gas. The strategy may facilitate the development of new synthetic protocols for the efficient and sustainable production of chemicals in an atom-economic way from simple, abundant starting materials.

1 aMidya, Siba, Prasad1 aSahoo, Manoj, Kumar1 aLandge, Vinod, Gokulkrish1 aRajamohanan, P., R.1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/reversed-reactivity-anilines-alkynes-rhodium-catalysed-c-h-activationcarbonylation-tandem00771nas a2200157 4500008004100000245005800041210005600099260000800155300001400163490000600177520026100183100003000444700002400474700002500498856009000523 2015 eng d00aReverse-hydroformylation: a missing reaction explored0 aReversehydroformylation a missing reaction explored cAUG a1422-14240 v23 a

Recent progress in transition-metal catalysed acceptor- and acceptorless-reverse hydroformylation of aldehydes for the conversion of olefins has been discussed. The aldehyde feedstock serves as a source for production of syngas and valuable alkenes.

1 aNandakumar, Avanashiappan1 aSahoo, Manoj, Kumar1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/reverse-hydroformylation-missing-reaction-explored01207nas 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-co201362nas 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

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.

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-n01316nas a2200157 4500008004100000022001400041245011600055210006900171260000900240300001400249490000700263520071100270100002100981700002501002856013101027 2019 eng d a1463-926200aRoom temperature catalytic dehydrogenation of cyclic amines with the liberation of H-2 using water as a solvent0 aRoom temperature catalytic dehydrogenation of cyclic amines with cAPR  a2119-21280 v213 a

Catalytic dehydrogenation of cyclic amines, in particular partially saturated N-heterocycles to N-heterocyclic arenes, with the removal of molecular hydrogen as the sole byproduct in water is reported. This dehydrogenation reaction proceeds smoothly under very mild and benign conditions and operates at room temperature. This distinctive reactivity has been achieved under dual catalytic conditions by merging the visible-light active [Ru(bpy)(3)](2+) as the photoredox catalyst and a newly synthesized cobalt complex as the proton-reduction catalyst. A detailed mechanistic study (control experiments, electrochemical studies, UV-visible experiments) is presented for the present dual catalysis.

1 aSahoo, Manoj, K.1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/room-temperature-catalytic-dehydrogenation-cyclic-amines-liberation-h-2-using-water-solvent02732nas 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.1c03283