00772nas a2200193 4500008004100000245015200041210006900193260000800262300001600270490000700286100002200293700002000315700001700335700002300352700002200375700002400397700002100421856013600442 2016 eng d00aAu(I)/Ag(I) co-operative catalysis: interception of Ag-bound carbocations with α-gold(I) enals in the imino-alkyne cyclizations with N-allenamides0 aAuIAgI cooperative catalysis interception of Agbound carbocation cNOV a14462-144650 v521 aBagle, Pradip, N.1 aMane, Manoj, V.1 aVanka, Kumar1 aShinde, Dinesh, R.1 aShaikh, Samir, R.1 aGonnade, Rajesh, G.1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/auiagi-co-operative-catalysis-interception-ag-bound-carbocations-%CE%B1-goldi-enals-imino-alkyne01330nas 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-benzylamines01032nas a2200169 4500008004100000022001400041245011500055210006900170260007100239300001400310490000700324520033800331100002200669700002300691700002100714856012700735 2016 eng d a1523-706000aGold vs rhodium catalysis: tuning reactivity through catalyst control in the C-H alkynylation of isoquinolones0 aGold vs rhodium catalysis tuning reactivity through catalyst con a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAR a1056-10590 v183 a

A site-selective C-4/C-8 alkynylation of isoquinolones catalyzed by gold and rhodium complexes is reported. A broad range of synthetically useful functional groups (-F, -Cl, -Br, -CF3, -OMe, alkyl, etc.) were tolerated, providing an efficient and robust protocol for the synthesis either C-4- or C-8-alkynylated isoquinolones.

1 aShaikh, Aslam, C.1 aShinde, Dinesh, R.1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/gold-vs-rhodium-catalysis-tuning-reactivity-through-catalyst-control-c-h-alkynylation-001917nas a2200181 4500008004100000245011400041210006900155260000800224300001200232490000600244520124400250100002901494700002401523700002301547700001901570700002101589856012501610 2016 eng d00aNew dinor-cis-labdane diterpene and flavonoids with antimycobacterium activity from colebrookea oppositifolia0 aNew dinorcislabdane diterpene and flavonoids with antimycobacter cMAR ae20-e240 v33 a

The new 14,15-dinor-cis-labdane diterpene, named (+)-14,15-dinor-9α-hydroxy-cis-labd-11(E)-en-13-one (1), was isolated from the acetone extract of the aerial parts of Colebrookea oppositifolia, along with the known compounds alnustin (2), mosloflavone (3), flindulatin (4), 5,6,7-trimethoxy baicalein (5), tanetin (6), scutellarein 4′-methyl ether (7), apigenin (8), caffeic acid (9), anisofolin A (10), apigetrin (11), and forsythoside A (12). Structures of the new and known compounds were established by detailed analysis of 1D and 2D nuclear magnetic resonance studies. The isolated compounds 1–12 were evaluated for their antimycobacterium activity against Mycobacterium tuberculosis H37Ra and Mycobacterium bovis in both dormant and active phases. Compounds 1, 7, and 8 exhibited inhibitory activity against M. tuberculosis with IC50 values in the range of 8.1–55.0 µM (MIC 14.4–119.7 µM) in the active phase and 7.4–43.5 µM (MIC 11.5–123.3 µM) in the dormant phase. Similarly 1, 7, and 8 exhibited inhibitory activity against M. bovis with IC50 values in the range of 4.1–98.5 µM (MIC 13.7–161.0 µM) in the active phase and 4.1–111.1 µM (MIC 13.0–166.4 µM) in the dormant phase.

1 aChinchansure, Ashish, A.1 aArkile, Manisha, A.1 aShinde, Dinesh, R.1 aSarkar, Dhiman1 aJoshi, Swati, P. uhttps://library.ncl.res.in/content/new-dinor-cis-labdane-diterpene-and-flavonoids-antimycobacterium-activity-colebrookea01436nas a2200229 4500008004100000022001400041245010700055210006900162260011000231300001600341490000600357520050500363100002200868700003300890700002200923700001900945700002300964700002400987700003501011700002801046856013201074 2016 eng d a2046-206900aResidue dependent hydrogen-bonding preferences in orthanilic acid-based short peptide beta-turn motifs0 aResidue dependent hydrogenbonding preferences in orthanilic acid aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a35328-353310 v63 a

This communication describes the competition between native beta-turn (C10) and 2-aminobenzenesulfonic acid (SAnt)( orthanilic acid)-based pseudo beta-turn (C11) in their hybrid peptides. Solid-state crystal structure and solution-state NMR studies revealed that C10 and C11 can be simultaneously observed under appropriate conditions. The variable temperature NMR coefficient data suggest that the isolated C11/C14 hydrogen bond is weaker in comparison with the consecutive C10 and C11 turns.

1 aJedhe, Ganesh, S.1 aVijayadas, Kuruppanthara, N.1 aKotmale, Amol, S.1 aSangtani, Ekta1 aShinde, Dinesh, R.1 aGonnade, Rajesh, G.1 aRajamohanan, Pattuparambil, R.1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/residue-dependent-hydrogen-bonding-preferences-orthanilic-acid-based-short-peptide-beta-turn01184nas a2200193 4500008004100000245010500041210006900146260000800215300001400223490000700237520047500244100002000719700002300739700002200762700002300784700002400807700002800831856013100859 2017 eng d00aCoumarin-appended stable fluorescent self-complementary quadruple-hydrogen-bonded molecular duplexes0 aCoumarinappended stable fluorescent selfcomplementary quadrupleh cJUN a6403-64080 v823 aIn this paper we report a coumarin-conjugated self-assembling system adorned with valuable features such as high duplex stability and a built-in fluorophore, which would augment its application potential. This system forms a highly :stalik molecular duplex in a nonpolar solvent (K-dim > 1.9 X 10(7) M-1 in CDCl3). Due to the fluorescent property of coumarin, these new structural motifs may find potential application in material chemistry and supramolecular chemistry.1 aKheria, Sanjeev1 aRayavarapu, Suresh1 aKotmale, Amol, S.1 aShinde, Dinesh, R.1 aGonnade, Rajesh, G.1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/coumarin-appended-stable-fluorescent-self-complementary-quadruple-hydrogen-bonded-molecular02517nas a2200205 4500008004100000245015200041210006900193260000800262300001600270490000700286520173400293100002102027700001702048700002302065700002502088700002202113700002402135700002402159856012802183 2017 eng d00aH-Bonding assisted self-assembly of anionic and neutral ligand on metal: a comprehensive strategy to mimic ditopic ligands in olefin polymerization0 aHBonding assisted selfassembly of anionic and neutral ligand on  cOCT a12448-124560 v563 aSelf-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC6H4-NH(CO)NH2}{Ph2PC6H4NH(CO)NH2}PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC6H4NH(CO)NHPh}{Ph2PC6H4NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 degrees C.1 aMote, Nilesh, R.1 aPatel, Ketan1 aShinde, Dinesh, R.1 aGaikwad, Shahaji, R.1 aKoshti, Vijay, S.1 aGonnade, Rajesh, G.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/h-bonding-assisted-self-assembly-anionic-and-neutral-ligand-metal-comprehensive-strategy01629nas a2200157 4500008004100000245006000041210006000101260000800161300001400169490000600183520112100189100002201310700002301332700002401355856009201379 2017 eng d00aIsomerizing hydroformylation of cashew nut shell liquid0 aIsomerizing hydroformylation of cashew nut shell liquid cOCT a3997-40040 v93 aA small library of bisphosphorus ligands was evaluated in the rhodium-catalyzed isomerizing hydroformylation (I-HF) of cashew nut shell liquid (CNSL). The rhodium complex of 1,2-bis((di-tert-butylphosphanyl)methyl)benzene (BDTBPMB; L4) outperformed the other bisphosphite and bisphosphine ligands and unveiled a moderate selectivity of 28% and 50% in the I-HF of CNSL monoene and methoxy-protected monoene, respectively. The resultant aldehyde 16-(3-methoxyphenyl)hexadecanal P1 was isolated and its identity was fully established. Application of bis-phosphine ligand L4 in the I-HF of highly challenging CNSL cardanol (S3) and methoxy-protected CNSL cardanol yielded a linear selectivity of 74%, although with reduced conversion. To demonstrate the synthetic utility of our strategy, the obtained aldehyde (derived from S3) was subjected to hydrogenation and the resultant 3-(16-hydroxyhexadecyl) phenol (P8) was isolated in 89% isolated yield. High-pressure NMR investigation revealed selective formation of a bis-equatorial BDTBPMB-rhodium complex, which might be responsible for the excellent linear selectivity.1 aPandey, Swechchha1 aShinde, Dinesh, R.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/isomerizing-hydroformylation-cashew-nut-shell-liquid01771nas a2200181 4500008004100000245011100041210006900152260000800221300001600229490000700245520108800252100002301340700002001363700002301383700002401406700002801430856013101458 2017 eng d00aModular approach towards functionalized highly stable self-complementary quadruple hydrogen bonded systems0 aModular approach towards functionalized highly stable selfcomple cDEC a10087-100940 v153 aSelf-complementary quadruple hydrogen bonded systems have shown potential as key building blocks for developing various supramolecular polymers. Opportunities for the introduction of multiple functionalities would further augment, in principle, their application potential. Herein, we report a novel modular approach to simultaneously introduce two closely aligned side chains into AADD-type self-complementary quadruple hydrogen-bonding systems. Dithiane-tethered ureidopyrimidinone has been used as a reactive intermediate to efficiently attach closely aligned side chains by simply reacting with amines to form highly stable molecular duplexes. These duplexes featuring AADD-type arrays of hydrogen bonding codes are highly stable in non-polar solvents (K-dim > 1.9 x 10(7) M-1 in CDCl3) as well as in polar solvents (K-dim > 10(5) in 10% DMSO-d(6)/CDCl3). Another notable feature of these self-assembling systems is their insensitivity to prototropy-related issues owing to their prototropic degeneracy, which will enhance their application potential in supramolecular chemistry.1 aRayavarapu, Suresh1 aKheria, Sanjeev1 aShinde, Dinesh, R.1 aGonnade, Rajesh, G.1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/modular-approach-towards-functionalized-highly-stable-self-complementary-quadruple-hydrogen02690nas a2200229 4500008004100000022001400041245011000055210006900165260000900234300001400243490000800257520190300265100002202168700001502190700002302205700001702228700002402245700002402269700001802293700002402311856012502335 2018 eng d a0002-786300aIron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process0 aIron Catalyzed Hydroformylation of Alkenes under Mild Conditions cMAR  a4430-44390 v1403 a

Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 degrees C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)(4)](-)[Ph3PNPPh3](+) (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)(2)(PPh3)(2)] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.

1 aPandey, Swechchha1 aRaj, Vipin1 aShinde, Dinesh, R.1 aVanka, Kumar1 aKashyap, Varchaswal1 aKurungot, Sreekumar1 aVinod, C., P.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/iron-catalyzed-hydroformylation-alkenes-under-mild-conditions-evidence-feii-catalyzed01300nas a2200205 4500008004100000245017600041210006900217260000800286300001400294490000700308520050000315100002400815700002300839700001600862700002400878700002200902700002400924700001900948856012700967 2018 eng d00aUnravelling the nucleophilicity of buten tides for 1,6-conjugate addition to p-quinone methides: a direct access to diversely substituted butenolide-derived diarylmethanes0 aUnravelling the nucleophilicity of buten tides for 16conjugate a cMAY a2787-27910 v203 aA Lewis acid catalyzed regioselective C-C bond is constructed through beta-addition of deconjugated butenolides with p-quinone methides in a 1,6-conjugate addition manner. Interestingly, Lewis acid catalyzed vinylogous Mukaiyama-Michael reaction of silyloxyfurans with p-QMs proceeds selectively through the alpha or gamma position exclusively. The reaction is mild with broad substrate scope, thus allowing easy access to a wide range of bis-arylated alpha-/beta-/gamma-substituted butenolides.1 aSharma, Brijesh, M.1 aShinde, Dinesh, R.1 aJain, Ruchi1 aBegari, Eeshwaraiah1 aSatbhaiya, Shruti1 aGonnade, Rajesh, G.1 aKumar, Pradeep uhttps://library.ncl.res.in/content/unravelling-nucleophilicity-buten-tides-16-conjugate-addition-p-quinone-methides-direct01140nas a2200193 4500008004100000022001400041245015400055210006900209260000800278300001400286490000700300520040300307100002400710700001800734700002300752700002600775700001500801856013000816 2023 eng d a2052-412900aSynthesis of N-functionalized 2,3-disubstituted benzofurans/naphthofurans from para-quinone methides and isocyanides via the [4+1] annulation pathway0 aSynthesis of Nfunctionalized 23disubstituted benzofuransnaphthof cJUL a3746-37510 v103 a

A scandium triflate catalyzed [4 + 1] cycloaddition reaction of 2-hydroxy-substituted para-quinone methides and isocyanides has been developed. This operationally simple, efficient and practical protocol provides straightforward access to a variety of N-functionalized 2,3-disubstituted benzofuran/naphthofuran derivatives with broad functional group compatibility and good scalability.

1 aKale, Someshwar, B.1 aKumar, Manish1 aShinde, Dinesh, R.1 aKrishna, Gamidi, Rama1 aDas, Utpal uhttps://library.ncl.res.in/content/synthesis-n-functionalized-23-disubstituted-benzofuransnaphthofurans-para-quinone-methides01258nas a2200169 4500008004100000022001400041245014400055210006900199260000900268300001400277490000700291520058000298100002300878700002600901700002600927856013500953 2024 eng d a0022-326300aMetal-free one-pot domino synthesis of oxazolidinethione derivatives of quaternary amino acids from α-amino esters and aldehydes using CS20 aMetalfree onepot domino synthesis of oxazolidinethione derivativ cFEB  a7109-71140 v893 a

We present a streamlined, metal-free, one-pot domino approach to efficiently synthesize oxazolidinethione derivatives containing substituted quaternary amino acids. This method employs alpha-amino esters, aldehydes, and CS2 under mild conditions, constructing three new bonds (C-N, C-C, and C-O) to produce oxazolidinethione compounds featuring a quaternary center and a beta-hydroxy derivative in high yields. This scalable protocol enables the creation of libraries of biologically significant, intricate amino acid derivatives using amino esters and aldehydes.

1 aShinde, Dinesh, R.1 aKrishna, Gamidi, Rama1 aMarelli, Udaya, Kiran uhttps://library.ncl.res.in/content/metal-free-one-pot-domino-synthesis-oxazolidinethione-derivatives-quaternary-amino-acids-%CE%B101658nas a2200169 4500008004100000022001400041245010400055210006900159260000900228300001400237490000700251520102100258100002301279700002901302700002601331856013101357 2025 eng d a1523-706000aPeptide functionalization with dithioate and trithioate groups: A CS2-mediated solid-phase approach0 aPeptide functionalization with dithioate and trithioate groups A cMAY  a6271-62780 v273 a

The dithiocarbamate group is an important class of compounds whose presence in small molecules and peptides leads to antimicrobial, anticancer, and enzyme inhibition properties. This study introduces an efficient and selective method for incorporating dithioate and trithioate moieties into amino acids and peptides using CS2 chemistry under mild conditions. Utilizing a N,N-diisopropylethylamine (DIPEA)-CS2-benzyl chloride system, we achieved modifications at the N-terminal amines and the side chains of Lys and Cys residues through solid-phase peptide synthesis (spps). The method exhibits excellent yields and broad compatibility with diverse amino acids, their protection groups, peptide chemistry reagents, and varied peptide sequences. Notably, the successful incorporation of trithioate groups into peptides via cysteines, reported here for the first time, expands the functional repertoire of peptide chemistry, offering new possibilities for peptide-based drug design and related applications.

1 aShinde, Dinesh, R.1 aBodake, Supriya, Mahadev1 aMarelli, Udaya, Kiran uhttps://library.ncl.res.in/content/peptide-functionalization-dithioate-and-trithioate-groups-cs2-mediated-solid-phase-approach