@article { ISI:000275049800051, title = {Structural diversity in partially fluorinated metal organic frameworks (F-MOFs) composed of divalent transition metals, 1,10-phenanthroline, and fluorinated carboxylic acid}, journal = {Crystal Growth \& Design}, volume = {10}, number = {3}, year = {2010}, month = {MAR}, pages = {1351-1363}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Seven new partially fluorinated metal-organic frameworks (F-MOFs) have been synthesized under different solvothermal conditions (H(2)O or N,N-dimethylformamide (DMF)) from transition metal cations [Zn(II), Co(II), and Mn(II)], 1,10-phenanthroline (phen), and 4,4{\textquoteright}-(hexafluoroisopropylidene) bis(benzoic acid) (C(17)H(10)F(6)O(4), H(2)hfbba) to determine the influence of reaction conditions on the formation of metal-organic frameworks. This family of materials displays a striking degree of structural similarity depending on the solvent of synthesis. Of the seven materials, two contain three-dimensional connectivity: Co(3)(hfbba)(6)(phen)(2) (F-MOF-6) and Mn(3)(hfbba)(6)(Phen)(2) (F-MOF-10). Three materials are one-dimensional structures: Zn(hfbba)(0.5)(phen)(HCO(2)) (F-MOF-8), Mn(Hhfbba)(2)(Phen) (F-MOF-11), and [Mn(hfbba)(2)(dm-phen)]center dot(H(2)O) (F-MOF-11A). Lastly, Co(hfbba)(phell)(2)center dot 2(H(2)hfbba)(H(2)O)(HCO(2)) (F-MOF-7) and Zn(hfbba)(phen)(2)center dot 2(H(2)hfbba) (H(2)O)-(HCO(2)) (F-MOF-9) are discrete zero-dimensional molecular complexes. F-MOF-6 and -10, which feature it three-dimensional (3D) framework with pcu topolgy are formed in DMF like F-MOF-8 and at 85 degrees C. The remaining F-MOFs are formed by a solvothermal reaction at 120 degrees C in water. F-MOF-7 and -9 are isostructural discrete zero-dimensional molecular complexes (a similar to 19.5; b similar to 13.7; c similar to 26.2/29.6 angstrom; beta similar to 99.9/120.04; V similar to 6840 angstrom(3)). All these F-MOFs were structurally determined by single-crystal X-ray diffraction. Solid-state properties such its UV-vis and the thermal stability of F-MOF-6 to -11A have also been studied. Insight into the factors influencing the preferred crystallization of a specific complex over others has been obtained from full quantum chemical (QM) calculations using density functional theory (DFT).

}, issn = {1528-7483}, doi = {10.1021/cg9013812}, author = {Pachfule, Pradip and Dey, Chandan and Panda, Tamas and Vanka, Kumar and Banerjee, Rahul} } @article { ISI:000313985200009, title = {Solving the problem of negative populations in approximate accelerated stochastic simulations using the representative reaction approach}, journal = {Journal of Computational Chemistry}, volume = {34}, number = {5}, year = {2013}, month = {FEB}, pages = {394-404}, publisher = {WILEY-BLACKWELL}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

Methods based on the stochastic formulation of chemical kinetics have the potential to accurately reproduce the dynamical behavior of various biochemical systems of interest. However, the computational expense makes them impractical for the study of real systems. Attempts to render these methods practical have led to the development of accelerated methods, where the reaction numbers are modeled by Poisson random numbers. However, for certain systems, such methods give rise to physically unrealistic negative numbers for species populations. The methods which make use of binomial variables, in place of Poisson random numbers, have since become popular, and have been partially successful in addressing this problem. In this manuscript, the development of two new computational methods, based on the representative reaction approach (RRA), has been discussed. The new methods endeavor to solve the problem of negative numbers, by making use of tools like the stochastic simulation algorithm and the binomial method, in conjunction with the RRA. It is found that these newly developed methods perform better than other binomial methods used for stochastic simulations, in resolving the problem of negative populations. (C) 2012 Wiley Periodicals, Inc.

}, keywords = {approximate methods, binomial distributions, Gillespie algorithm, Kinetic Monte Carlo, Poisson distributions, representative reaction approach, Stochastic simulations}, issn = {0192-8651}, doi = {10.1002/jcc.23158}, author = {Kadam, Shantanu and Vanka, Kumar} } @article { ISI:000316693100020, title = {Synthesis of palmyrolide A and its cis-isomer and mechanistic insight into trans-cis isomerisation of the enamide macrocycle}, journal = {Chemical Communications}, volume = {49}, number = {32}, year = {2013}, month = {MAR}, pages = {3342-3344}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Concise and protecting-group free synthesis of ent-palmyrolide A and (-)-cis-palmyrolide A were achieved starting from commercially available (S)-citronellal. The key fragment of palmyrolide A, {\textquoteleft}{\textquoteleft}(5S,7S)-7-hydroxy-5,8,8-trimethylnonanamide{\textquoteright}{\textquoteright}, which makes up the most challenging part of the target molecule, was prepared in just three steps. A plausible mechanism for the trans-cis isomerization of the double bond in the macrocycle has been investigated.

}, issn = {1359-7345}, doi = {10.1039/c3cc40541a}, author = {Philkhana, Satish Chandra and Seetharamsingh, B. and Dangat, Yuvraj B. and Vanka, Kumar and Reddy, D. Srinivasa} } @article { ISI:000340525300012, title = {Synthesis of alpha,beta-unsaturated delta-lactones by vinyl acetate mediated asymmetric cross-aldol reaction of acetaldehyde: mechanistic insights}, journal = {European Journal of Organic Chemistry}, number = {24}, year = {2014}, month = {AUG}, pages = {5247-5255}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

A tandem asymmetric cross-aldol reaction involving the in situ generation of acetaldehyde from vinyl acetate has been developed that may resolve the challenges associated with the handling of acetaldehyde. The simple protocol, mild reaction conditions and unique harmony of an organocatalyst with a biocatalyst make this method a valuable tool for the synthesis of asymmetric beta-hydroxy aldehydes. By using this methodology we have accessed alpha,beta-unstaurated delta-lactones as well as isochromenones with high enantioselectivities from both asymmetric beta-hydroxy aldehydes and ketones. Systemic density functional theory (DFT) studies were also performed to gain mechanistic insights into the role of hydrogen bonding in the asymmetric cross-aldol reaction of acetaldehyde and in the key cis/trans isomerisation step in the synthesis of d-lactones.

}, keywords = {Aldol reactions, asymmetric catalysis, lactones, reaction mechanisms}, issn = {1434-193X}, doi = {10.1002/ejoc.201402551}, author = {Kumar, Manjeet and Kumar, Arvind and Rizvi, Masood and Mane, Manoj and Vanka, Kumar and Taneja, Subhash C. and Shah, Bhahwal Ali} } @article { ISI:000350221600066, title = {Silica microspheres containing high density surface hydroxyl groups as efficient epoxidation catalysts}, journal = {RSC Advances}, volume = {5}, number = {27}, year = {2015}, month = {FEB}, pages = {21125-21131}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

Uniformly sized silica microspheres were synthesized by a hydrolysis-condensation method. The obtained material was etched with a mild aqueous potassium hydroxide solution for different periods of time to break their Si-O-Si bonds and increases the density of hydroxyl groups on their surfaces. The resulting materials were then used as transition metal-free catalysts for oxidation of olefins in the presence of hydrogen peroxide as a green oxidant. The materials were thoroughly characterized using various physicochemical techniques. These highly populated hydroxyl groups on the surface of silica microspheres were proven to be responsible for excellent conversion (up to 93\%) and epoxide selectivity (up to 100\%) for various olefins. Quantum mechanical calculations also corroborate the experimental findings. Furthermore, both experimental and theoretical studies show that tertiary silanols were present at the active sites of the catalyst surface and were responsible for olefin epoxidation.

}, issn = {2046-2069}, doi = {10.1039/c5ra00374a}, author = {Chandra, Prakash and Doke, Dhananjay S. and Shubhangi B. Umbarkar and Vanka, Kumar and Biradar, Ankush V.} } @article { ISI:000369211700025, title = {Small molecule activation by constrained phosphorus compounds: insights from theory}, journal = {Inorganic Chemistry}, volume = {55}, number = {2}, year = {2016}, month = {JAN}, pages = {558-565}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

An exciting new development in main group chemistry has been the use of a constrained, flat, phosphorus-based complex to mediate in reactions such as the dehydrogenation of ammonia borane (AB), and the activation of the NH bond in primary amines. Its importance is based on the fact that it shows that main group compounds, when properly designed, can be as effective as transition metal complexes for doing significant chemical transformations. What the current computational study, employing density functional theory (DFT), reveals is that a common, general mechanism exists that accounts for the behavior of the flat phosphorus compound in the different reactions that have been experimentally reported to date. This mechanism, which involves the mediation by a base as a proton transfer agent, is simpler and energetically more favorable than the previous mechanisms that have been proposed for the same reactions in the literature. It is likely that the knowledge gained from the current work about the chemical behavior of this phosphorus compound can be utilized to design new constrained phosphorus-based compounds.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.5b01074}, author = {Pal, Amrita and Vanka, Kumar} } @article {43726, title = {Secondary interactions arrest the hemiaminal intermediate to invert the modus operandi of schiff base reaction: a route to benzoxazinones}, journal = {Journal of Organic Chemistry}, volume = {82}, year = {2017}, month = {APR}, pages = {4342-4351}, type = {Article}, abstract = {Discovered by Hugo Schiff, condensation between amine and aldehyde represents one of the most ubiquitous reactions in chemistry. This classical reaction is widely used to manufacture pharmaceuticals and fine chemicals. However, the rapid and reversible formation of Schiff base prohibits formation of alternative products, of which benzoxazinones are an important class. Therefore, manipulating the reactivity of two partners to invert the course of this reaction is an elusive target. Presented here is a synthetic strategy that regulates the sequence of Schiff base reaction via weak secondary interactions. Guided by the computational models, reaction between 2,3,4,5,6-pentafluoro-benzaldehyde with 2-amino-6methylbenzoic acid revealed quantitative (99\%) formation of 5-methyl-2-(perfluoropheny01,2-dihydro-4H-benzo[d][1,3]oxazin-4-one (15). Electron donating and electron withdrawing ortho-substituents on 2-aminobenzoic acid resulted in the production of benzoxazinones 936. The mode of action was tracked using low temperature NMR, IN vis spectroscopy, and isotopic (O-18) labeling experiments. These spectroscopic mechanistic investigations revealed that the hemiaminal intermediate is arrested by the hydrogen-bonding motif to yield benzoxazinone. Thus, the mechanistic investigations and DFT calculations categorically rule out the possibility of in situ imine formation followed by ring-closing, but support instead hydrogen-bond assisted ring-closing to prodrugs. This unprecedented reaction represents an interesting and competitive alternative to metal catalyzed and classical methods of preparing benzoxazinone.}, doi = {10.1021/acs.joc.7b00352}, author = {Patel, Ketan and Deshmukh, Satej S. and Bodkhe, Dnyaneshwar and Mane, Manoj and Vanka, Kumar and Shinde, Dinesh and Rajamohanan, Pattuparambil R. and Nandi, Shyamapada and Vaidhyanathan, Ramanathan and Chikkali, Samir H.} } @article {46159, title = {Silylene induced cooperative B-H bond activation and unprecedented aldehyde C-H bond splitting with amidinate ring expansion}, journal = {Chemical Communications}, volume = {55}, year = {2019}, month = {MAR }, pages = {3536-3539}, type = {Article}, abstract = {

The addition of HBpin to PhC(NtBu)(2)SiN(SiMe3)(2) (1) results in the cleavage of the B-H bond in a cooperative fashion across the Si and amidinate-C sites. The reaction of 1 with benzaldehyde led to C-H bond activation with amidinate ring expansion leading to a five-membered heterocycle. In case of 4-fluorobenzaldehyde, a C-C bond coupling takes place leading to a dioxasilolane derivative as the major product.

}, issn = {1359-7345}, doi = {10.1039/c9cc00296k}, author = {Swamy, V. S. V. S. N. and Raj, K. Vipin and Vanka, Kumar and Sen, Sakya S. and Roesky, Herbert W.} } @article {46248, title = { Synthesis and reactivity of a hypersilylsilylene }, journal = {Inorganic chemistry}, volume = {58}, year = {2019}, month = {AUG}, pages = {10536-10542}, type = {Article}, abstract = {

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized with the preparation of PhC(NtBu)(2)Si{Si(SiMe3)(3)} (1) from PhC(NtBu)(2)SiHCl2 with K{Si(SiMe3)(3)} in more than 90\% yield. The highly deshielded Si-29 NMR resonance (delta = 76.91 ppm) can be attributed to the absence of a pi-donating substituent. The molecular structure of 1 shows a trigonal-planar geometry around the Si-II center with a Si-II-Si-IV bond length of 2.4339(13) angstrom. A series of reactions of 1 with Me3NO, S, Se, and Te were performed. While siloxane derivatives (2 and 3) are obtained from reactions with Me3NO, silachalcogenones (4-6) are formed with other chalcogens. The presence of Si=E (E = S, Se, and Te) bonds in 4-6 have been confirmed by single crystal X-ray studies. Silaoxirane (7) formation was observed when 1 was treated with acetone, demonstrating the importance of the tris(trimethylsilyl)silyl group to kinetically and thermodynamically protect the silaoxirane derivative with less bulky substituents on the C atom.

}, doi = {10.1021/acs.inorgchem.9b00418}, author = {Bisai, Milan Kumar and Swamy, V. S. V. S. N. and Das, Tamal and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {47382, title = {Substrate, catalyst, and solvent: the triune nature of multitasking reagents in hydroboration and cyanosilylation}, journal = {Organometallics}, volume = {40}, year = {2021}, month = {APR}, pages = {1104-1112}, type = {Article}, abstract = {

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.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.1c00070}, author = {Dixit, Ruchi and Bisai, Milan Kumar and Yadav, Sandeep and Yadav, Vinita and Sen, Sakya S. and Vanka, Kumar} } @article {47605, title = {Synthesis of four diastereomers of notoryne and their C-13 NMR chemical shifts analysis}, journal = {Journal of Chemical Sciences}, volume = {133}, year = {2021}, month = {SEP}, pages = {76}, type = {Article}, abstract = {In this manuscript we document the details of the synthesis of four diastereomers of notoryne. The synthesis of one of the diastereomer having a similar relative stereochemistry of substituents on the both THF rings like notoryne, however, being the relative stereochemistry between the bridging carbon of these two THF units is changed from anti to syn has been executed mainly to learn how the ring carbon chemical shifts vary with this change. Interestingly, the deviations are found mainly for the carbons of THF ring that bears the Br-group. In addition to this isomer, three more diastereomers having the relative stereochemistry of substituents on either of the THF rings varied have been also synthesized. All four diastereomers have been subjected for extensive NMR studies and their C-13 NMR chemical shifts have been compared with notoryne and laurendecumenyne B. In addition, chemical shifts for the four diastereomers along with these natural products were calculated with the help of DFT calculations and compared to the experimentally obtained chemical shift values.}, issn = {0974-3626}, doi = {10.1007/s12039-021-01929-y}, author = {Senapati, Sibadatta and Das, Shyamsundar and Dixit, Ruchi and Vanka, Kumar and Ramana, V, Chepuri} } @article {48405, title = {Silver dependent enantiodivergent gold(i) catalysed asymmetric intramolecular hydroamination of alkenes: a theoretical study}, journal = {Catalysts}, volume = {12}, year = {2022}, month = {NOV}, pages = {1392}, type = {Article}, abstract = {

We report a theoretical study of the first silver-dependent enantiodivergent gold-catalysed reaction. The combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate catalyses the asymmetric intramolecular hydroamination of alkenes and affords both enantiomers of the products by applying a simple solvent change from toluene to methanol. A gold-silver chloride adduct that occurs only in methanol appears to control the enantioinversion. If one gold atom coordinates and activates the alkene moiety, the other gold is included in an adduct with silver chloride, which coordinates a methanol solvent molecule and further interacts with the amine function. If the use of toluene implies free anions and affords (S)-enantiomer, methanol allows a proximal interaction with the amine, leads to an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and results in the (R)-enantiomer.

}, keywords = {alkene, enantiodivergent catalysis, Gold, hydroamination, Silver}, doi = {10.3390/catal12111392}, author = {Dixit, Ruchi and Sharma, Himanshu and Agbossou-Niedercorn, Francine and Vanka, Kumar and Michon, Christophe} } @article {47834, title = {Silver-catalyzed [3 + 3]-annulation cascade of alkynyl alcohols and α,β-unsaturated ketones for the regioselective assembly of chromanes}, journal = {Organic Chemistry Frontiers}, volume = {9}, year = {2022}, month = {JAN}, pages = {802-809}, type = {Article}, abstract = {An unprecedented Ag(i)-catalyzed [3 + 3]-annulation of alkynyl alcohols (5-hexyn-1-ols) and α,β-unsaturated ketones is reported to construct simple to complex chromanes. This transformation begins with hydroalkoxylation of alkynol through C{\textendash}C triple bond activation to give cyclic-enol ether, followed by intermolecular 1,4-addition and intramolecular 1,2-addition of enol ethers onto the enone and oxidative aromatization or Grob-type elimination steps. Facile reaction conditions, broad substrate scope, good to excellent yields, and atom economy are the salient features of this protocol. Isolation of the active pyran-tethered cyclohexadiene reaction intermediate, additional supporting experiments, and DFT calculations strongly support the experimental findings and corroborate our proposed mechanism.}, issn = {2052-4129}, doi = {10.1039/D1QO01643A}, author = {Nakate, Ashwini K. and Thorat, Sagar S. and Jain, Shailja and Rama Krishna, Gamidi and Vanka, Kumar and Kontham, Ravindar} } @article {48149, title = {Substitution at sp(3) boron of a six-membered NHC center dot BH3: convenient access to a dihydroxyborenium cation}, journal = {Chemical Communications}, volume = {58}, year = {2022}, month = {MAR }, pages = {3783-3786}, type = {Article}, abstract = {

Herein, we have undertaken the synthesis and investigated the reactivity of a 6-membered saturated NHC borane adduct (1). Direct electrophilic halogenation of 1 with a stoichiometric amount of I-2 led to NHC boryl iodides, 6-SIDipp center dot BH2I (2) and 6-SIDipp center dot BHI2 (3), which were further reacted with various nucleophiles to give novel 6-SIDipp based mono and disubstituted boranes with OTf (4 and 6) or ONO2 (5 and 7) functional groups. The addition of Br-2/H2O to 1 smoothly results in a dihydroxyborenium cation (8).

}, issn = {1359-7345}, doi = {10.1039/d1cc06816d}, author = {Kundu, Gargi and Ajithkumar, V. S. and Raj, K. Vipin and Vanka, Kumar and Tothadi, Srinu and Sen, Sakya S.} } @article {48738, title = {Six-membered NHC stabilized monomeric zinc complexes}, journal = {European Journal of Inorganic Chemistry}, volume = {26}, year = {2023}, month = {JUL}, pages = {e202300167}, type = {Article}, abstract = {

This paper describes the rare use of a 6-membered saturated N-heterocyclic carbene (NHC) known as 1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene (abbreviated as 6-SI-Dipp) as a ligand in zinc chemistry. We report on the investigation of the reactions between 6-SI-Dipp and ZnX2, which resulted in a range of new monomeric 6-SIDipp center dot ZnX2 complexes (X=Et (1), Cl (2), Br (3), and I (4)). We also prepared a new NHC zinc complex where the two substituents of the zinc atom are different, 6-SIDipp center dot Zn(Et)Br (7) through the reaction of the proligand [6-SIDippH]Br with ZnEt2. We have observed that the reactions of complex 1 with sulfur and HBpin led to the removal of the ZnEt2 moiety, resulting in the formation of a C=S double bond and a B H activation product, respectively. Lastly, the reaction of 1 with five-membered NHCs led to the exchange of carbene and the formation of either 5-IDipp center dot ZnEt2 (8) or 5-SIDipp center dot ZnEt2 (9).

}, keywords = {Lewis adduct, NHC, X-ray diffraction, zinc}, issn = {1434-1948}, doi = {10.1002/ejic.202300167}, author = {Gour, Kritika and Kundu, Gargi and Dash, Soumya Ranjan and Vanka, Kumar and Tothadi, Srinu and Sen, Sakya S.} } @article {48832, title = {Synthesis, characterization, crystal structure, in silico and computational studies on a novel Schiff base derived from α-chlorocinnamaldehyde and 4-aminoantipyrine}, journal = {Journal of Molecular Structure}, volume = {1289}, year = {2023}, month = {OCT}, pages = {135928}, type = {Article}, abstract = {

Schiff base, 4-(((1E,2Z)-2-chloro-3-phenylallylidene)amino)-1,5-dimethyl-2-phenyl-1,2 -dihydro-3H-pyrazol-3-one (1) was synthesized by condensation reaction of 4-aminoantipyrine and \& alpha;-chlorocinnamaldehyde. The compound was characterized using Fourier-transform infrared spectroscopy (FT-IR), ultraviolet (UV)-visible spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy (1H/13C NMR) and single-crystal X-ray diffraction analysis (SC-XRD). Density functional theory (DFT) was used to compute molecular parameters and also compared them with experimental data. The X-ray diffraction data revealed that the compound crys-tallizes as a monoclinic crystal system with a space group of C2/c and Z = 8, and is stabilized by C12-H12MIDLINE HORIZONTAL ELLIPSISO1, and C8-H8AMIDLINE HORIZONTAL ELLIPSISO1 intramolecular hydrogen bonds. The presence of a distinctive azomethine C = N bond length N3-C12 of 1.283(3) \& ANGS;, and 1640 cm-1 stretching vibration in the FT-IR spectrum are evidence of the formation of a Schiff base. The computational result indicates that the ionization energy (IE), and electron affinity (EA) values for the molecule are 4.025 and 2.110 eV, respectively. The positive value of EA suggests that the addition of an electron to the molecule would be an exothermic process. The evaluated energy is relatively low and is an expression of the ease of electron transfer from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). Hirsfeld surface map over dnorm and curvedness surface indicated the presence of 7C-7C stacking while the shape factor index suggests donor and acceptor intermolecular C-H-7C. Analysis of Hirsfeld surfaces concerning the fingerprint indicated a minimal contribution from the de -di pair and reveals H{\textendash}H as a major contribution to the Hirsfeld surface. However, the molecular packing did not confirm H{\textendash}H as a significant contributor the packing. Docking calculations on the compound showed average theoretical binding energies toward aromatase (-5.99 \& PLUSMN; 0.34 kcal/mol) and fibroblast growth factor receptor (FGFR) (-17.57 \& PLUSMN; 6.85 kcal/mol), indicating binding interactions with both protein targets.

}, keywords = {Computational studies, molecular modeling, Schiff base, X-ray crystallography}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2023.135928}, author = {Adimudo, Hillary Chijioke and Agu, Chidike Justus and Okenyeka, Obinna U. and Eddy, Nnabuk O. and Dim, Ebubechukwu Nnamdi and Dege, Necmi and Bonardd, Sebastian and Vanka, Kumar and Ibezim, Akachukwu and Idika, Digbo Iku and Diaz, David Diaz and Obasi, Nnamdi Lawrence} } @article {48720, title = {Synthesis of Si(IV)- and Ge(II)-substituted amines, hydrazone, and hydrazine from hypersilyl germylene}, journal = {Organometallics}, volume = {42}, year = {2023}, month = {OCT}, pages = {2983-2990}, type = {Article}, abstract = {

This study investigates the reactivity of a hypersilyl germylene [PhC-(NtBu)(2)GeSi-(SiMe3)(3)] (1) with various organic compounds including azides, diazoalkanes, 1,2-diphenylhydrazine, and trifluoroacetophenone. The reactivity observed in these reactions is driven by the insertion of the organic fragment between a silicon and germanium bond. This leads to the formation of novel compounds, including an amine featuring three different substituents from three different elements of group 14. When reacting with Me3SiCHN2, we observed the insertion of the diazoalkane fragment in an end-on fashion into the Ge-Si bond. An analogous trend was observed in reactions with 1,2-diphenylhydrazine and trifluoroacetophenone, where the N-N and C-O fragments were inserted into the Ge-Si bond. Multinuclear NMR and single-crystal X-ray diffraction analyses were conducted to characterize the newly synthesized compounds.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.3c00318}, author = {Ajithkumar, V. S. and Ghanwat, Pratiksha B. and Raj, K. Vipin and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {49089, title = {Size matters: computational insights into the crowning of noble gas trioxides}, journal = {Inorganic Chemistry}, volume = {63}, year = {2024}, month = {FEB}, pages = {4099-4107}, type = {Article}, abstract = {

In pursuit of enhancing the stability of the highly explosive and shock-sensitive compound XeO3, we performed quantum chemical calculations to investigate its possible complexation with electron-rich crown ethers, including 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, and 21-crown-7, as well as their thio analogues. Furthermore, we expanded our study to other noble gas trioxides (NgO(3)), namely, KrO3 and ArO3. The basis set superposition error (BSSE) corrected interaction energies for these adducts range from -13.0 kcal/mol to -48.2 kcal/mol, which is notably high for sigma-hole-mediated noncovalent interactions. The formation of these adducts was observed to be more favorable with the increase in the ring size of the crowns and less favorable while going from XeO3 to ArO3. A comprehensive analysis by various computational tools such as the mapping of the electrostatic potential (ESP), Wiberg bond indices (WBIs), Bader{\textquoteright}s theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, noncovalent interaction (NCI) plots, and energy decomposition analysis (EDA) revealed that the C-H center dot center dot center dot O interactions, as well as dispersion interactions, play a pivotal role in stabilizing adducts involving larger crowns. A noteworthy outcome of our study is the revelation of a coordination number of 9 for xenon in the complex formed between XeO3 and the thio analogue of 18-crown-6, which is higher than the largest number reported to date.

}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.3c03782}, author = {Dash, Soumya Ranjan and Sharma, Himanshu and Tiwari, Mrityunjay K. and Greb, Lutz and Vanka, Kumar} } @article {49868, title = {Silylene-copper(i) catalysis: regioselective protoboration of terminal alkynes}, journal = {Chemical Communications}, volume = {61}, year = {2025}, month = {DEC}, pages = {19652-19655}, type = {Article}, abstract = {

Herein, we report an efficient regioselective protoboration of the terminal alkynes catalyzed by newly synthesized silylene-copper(i)-aryl complexes. This method offers a broad substrate scope, good functional-group compatibility, and a gram-scale synthetic ability. The insight into the mechanistic cycle is also provided with the support of experimental and theoretical studies.

}, issn = {1359-7345}, doi = {10.1039/d5cc06125c}, author = {Kaulage, Sandeep H. and Shah, Brij Kumar and Panday, Rishukumar and Sharma, Himanshu and Vanka, Kumar and Khan, Shabana} } @article {49507, title = {Studies on the stereoselective synthesis of sacubitril via a chiral amine transfer approach}, journal = {Chemistry-An Asian Journal}, volume = {20}, year = {2025}, month = {MAR }, type = {Article}, abstract = {

We present a comprehensive account of our efforts directed towards the synthesis of sacubitril, a neprilysin inhibitor used in combination with valsartan and marketed as Entresto (TM). Our initial approach to the formal synthesis of sacubitril employed a chiral pool strategy, utilizing (S)-pyroglutamic acid as a key building block and Cu(I)-mediated Csp2-Csp3 cross-coupling as a key transformation. Further investigations led to the development of chiral amine transfer (CAT) reagents-based stereoselective synthesis. This involved the E-selective construction of gamma-ylidene-butenolide from readily available biphenyl bromide and 4-pentynoic acid, the conversion of this butenolide to its ene-lactam using chiral amine, and substrate-controlled diastereoselective reduction of ene-lactam using Et3SiH or Pd/C, H2 (overall chiral amine transfer) as key transformations. Antipodal lactam intermediates were synthesized using corresponding chiral amines, and the stereochemical outcomes during the ene-lactam reduction with Et3SiH were rationalized by DFT studies.

}, keywords = {Chiral Amine Transfer (CAT) approach, Chiral pool approach, Sacubitril, stereoselective synthesis}, issn = {1861-4728}, doi = {10.1002/asia.202401223}, author = {Sadanande, Megha V. and Thorat, Sagar S. and Sharma, Himanshu and Singh, Geetika and Vanka, Kumar and Gonnade, Rajesh G. and Kontham, Ravindar} } @article {49527, title = {Synthesis and concomitant polymorphs of green fluorescence protein chromophore-anthracene-based fluorescent analogue}, journal = {Crystal Growth \& Design}, volume = {25}, year = {2025}, month = {FEB}, pages = {1011-1022}, type = {Article}, abstract = {

Controlled variations in fluorescence properties hold significant promise for applications in optical sensors, bioimaging, and advanced display devices. However, constructing multicolor fluorescent systems remains a challenge. In this study, we demonstrate the development of multicolor fluorescence by generating polymorphs of a novel green fluorescent protein chromophore analogue, which exhibits distinct photoluminescence emissions in the solid state. The observed emission variations are attributed to differences in molecular conformation due to variations in pi-stacking interactions between the polymorphs. This offers a novel approach to designing materials with tunable fluorescence properties.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.4c01347}, author = {Mali, Bhupendra P. and Dabke, Niteen B. and Dash, Soumya R. and Biswas, Anupam and Vanka, Kumar and Manoj, Kochunnoonny and Gonnade, Rajesh G.} } @article {49720, title = {Synthesis, crystal structure, DFT calculation and catalytic activity of a polymer complex of zinc(II) succinate with 2-amino-1,3,4-thiadiazole}, journal = {Journal of Molecular Structure}, volume = {1338}, year = {2025}, month = {AUG}, pages = {142274}, type = {Article}, abstract = {

A polymer complex of zinc(II) succinate with a 2-amino-1,3,4-thiadialole ligand, denoted as [Zn2L2(suc)2]n, was synthesized and characterized by NMR, ESI-MS, FTIR, and FT-Raman spectroscopy, TGA, and X-ray crystallography. The polymer complex crystallizes in the orthorhombic noncentrosymmetric Pna21 space group and features a five-coordinate zinc ion in a distorted spherical square pyramidal geometry. The Hirshfeld surface analysis was carried out to evaluate the intermolecular interactions. Additionally, computational studies were also conducted to assess the stability of the Zn polymer complex and analyze the electron density distribution of the HOMO and LUMO. The catalytic activity of our complex was tested, interestingly, that showed good results for Biginelli reactions with distinct substrate scope in good to high yield at mild reaction conditions.

}, keywords = {DFT, Dihydropyrimidinones, Polymer complex, succinate, Thiadiazole, zinc}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2025.142274}, author = {Nuralieva, Guzal and Alieva, Mushtariy and Torambetov, Batirbay and Leslee, Denzil Britto Christopher and Senthilkumar, Beeran and Kaur, Simranjeet and Dabke, Niteen B. and Vanka, Kumar and Ashurov, Jamshid and Kadirova, Shakhnoza and Gonnade, Rajesh G.} } @article {49683, title = {Synthesis of diamido N-heterocyclic imines (DAC = NH) via staudinger or reductive N-N bond cleavage approach}, journal = {Organometallics}, volume = {44}, year = {2025}, month = {MAY}, pages = {1129-1133}, type = {Article}, abstract = {

This report communicates the first examples of N-heterocyclic imines based on electrophilic diamido carbenes (DACs). While 2 is prepared by classical Staudinger synthesis, 4 is obtained via an unusual reductive N-N bond cleavage of an azine by HCl. The exocyclic C=N bond lengths in 2 and 4 are substantially shorter than those based on N-heterocyclic carbenes and cyclic (alkyl)(amino)carbene reflecting the electrophilic character of DACs.

}, issn = {0276-7333}, doi = {10.1021/acs.organomet.5c00120}, author = {Balayan, Kajal and Sharma, Himanshu and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.} } @article {50030, title = {Switchable solid-state emission in GFP chromophore analogue cocrystals via competing AIE and ACQ pathways}, journal = {CrystEngComm}, volume = {28}, year = {2026}, month = {MAR}, pages = {1775-1780}, type = {Article}, abstract = {

We present a crystal-engineering approach enabling switchable solid-state emission (green -\> orange -\> quenched) in GFP-chromophore analogue cocrystals. The coformer{\textquoteright}s electronic and supramolecular effect shifts the photophysical pathway: intramolecular CT in cocrystal-I (green) and cocrystal-III (quenched) and intermolecular CT in cocrystal-II, yielding orange emissions and highlighting cocrystallization{\textquoteright}s power for tunable luminophores.

}, doi = {10.1039/d6ce00041j}, author = {Mali, Bhupendra P. and Dabke, Niteen B. and Sharma, Himanshu and Dash, Soumya Ranjan and Manoj, Kochunnoonny and Vanka, Kumar and Gonnade, Rajesh G.} }