Department of Chemistry

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    Rhodium-Catalyzed Annulation of Vinylated Tyrosines with Internal Alkynes to Access Oxepine-Mounted Unnatural Tyrosines and Its Peptide Late Stage Functionalization
    (ACS, 2022-09) Sakhuja, Rajeev
    A Rh(III)-catalyzed [5+2] annulation of vinyl tyrosines with symmetrical and unsymmetrical internal alkynes was achieved, furnishing a series of oxepine-mounted tyrosine-based unnatural amino acids. In addition, the chemical applicability of the developed strategy was exemplified by stapling amino acid/peptide-appended alkynes with vinyl tyrosines and late stage functionalization of tyrosine-containing dipeptides and tripeptide with internal alkynes.
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    Phenyliodine(III) Diacetate-Mediated 1,2-ipso-Migration in Mannich Bases of Imidazo[1,2-a]pyridines: Preparation of N-Acetoxymethyl/Alkoxymethyl-N-arylimidazo[1,2-a]pyridine-3-amines
    (ACS, 2020-05) Kumar, Anil
    Phenyliodine(III) diacetate -mediated 1,2-ipso-migration of an imidazo[1,2-a]pyridine ring via the formation of an aziridine intermediate in Mannich bases derived from imidazo[1,2-a]pyridines, 2-pyridylamines or arylamines, and formaldehyde is reported. The imidazo[1,2-a]pyridines bearing different substituents showed excellent migratory aptitude and resulted in corresponding N-acetoxymethyl-, N-alkoxymethyl-, and N-hydroxymethyl-N-arylimidazo[1,2-a]pyridine-3-amine derivatives in moderate to excellent (42 examples; 35–93%) yields. Radical trapping experiments confirmed the involvement of a non-radical intermediate. The developed protocol is amenable for a scale-up reaction, and synthetic utility of N-acetoxymethyl products was demonstrated by transforming them to corresponding N-(pyridin-2-yl)imidazo[1,2-a]pyridin-3-amines
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    Mechanochemical Ruthenium-Catalyzed Ortho-Alkenylation of N-Heteroaryl Arenes with Alkynes under Ball-Milling Conditions
    (ACS, 2022-04) Kumar, Anil
    The mechanochemical, solvent-free Ru(II)-catalyzed alkenylation of N-heteroaryl arenes with alkynes has been successfully described. A wide spectrum of arenes bearing N-heteroaryl moieties such as imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine, benzo[d]imidazo[2,1-b]thiazole, imidazo[2,1-b]thiazole, 2H-indazole, 1H-indazole, 1H-pyrazole, and 1,2,4-oxadiazol-5(4H)-one as a directing group reacted with various substituted alkynes under ball milling in the presence of [Ru(p-cymene)Cl2]2, affording dialkenylated products in moderate to good yields. The reaction of 2,3-dihydrophthalazine-1,4-dione with 1-phenyl-1-propyne afforded a monoalkenylated product. Similarly, reaction of 2-phenylimidazo[1,2-a]pyridine with aliphatic terminal alkynes produced a monoalkenylated derivative as the major product along with minor amount of dialkenylated product. The developed method exhibited excellent functional group compatibility, broad substrate scope, shorter reaction times, and no external heating. Moreover, the method can be readily scaled-up as demonstrated by gram-scale synthesis of 2-(2,6-bis((E)1-phenylprop-1-en-2-yl)phenyl)imidazo[1,2-a]pyridine.
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    Deciphering the Photophysical Role of Conjugated Diyne in Butadiynyl Fluorophores: Synthesis, Photophysical and Theoretical Study
    (ACS, 2013-07) Pati, Avik K.
    The present work focuses on the current interest in diyne bridged chromophores necessitating a clearer understanding of the photophysics of such molecules. The significance of the diyne moiety in the photophysics has been investigated by synthesizing simple substituted diphenyl butadiynyl derivatives following a quick and efficient microwave assisted Eglinton coupling of terminal alkynes. Emission of the fluorophores is observed from the usual locally excited (LE) state and intramolecular charge transfer (ICT) state. Separation of pure ICT emission from pure LE emission has been carried out by Gaussian/Lorentzian curve fitting. The vibronic coupling in the local transitions appears to be confined to the normal mode involving the C–C triple bond stretching of the diyne moiety. This implies that the LE transition involves the diyne moiety, a conclusion supported by quantum chemical calculations. The resolved ICT emission follows double linear dependence on ET(30) solvent polarity scale. The important role of the diyne moiety in the photophysics of this class of molecules is clearly discernible in this study.
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    Photophysical Impact of Diacetylenic Conjugation on Classical Donor–Acceptor Electronic Energy Pair
    (ACS, 2018-12) Pati, Avik K.
    Organic fluorophores with extended π-conjugation are important for their widespread applications. The present work provides photophysical insights into a diacetylene bridged classical donor–acceptor electronic energy pair, naphthalene–pyrene, in comparison with its constituents’ molecular structures, naphthyl and pyrenyl acetylenes, as well as parent naphthalene and pyrene chromophores. The diacetylenic dye loses the individual spectral identities of the donor and acceptor fluorophores exhibiting a locally excited (LE) emission (∼411 nm) from the overall molecular entity with high fluorescence quantum yields (0.55–0.84) in nonaqueous media. In contrast to the parent pyrene, the hybrid derivative shows a strongly allowed S0 → S1 transition. In mixed-aqueous media, the dye forms aggregates displaying a new red-shifted absorption (∼425 nm) as well as emission (∼510 nm) band. Unlike the hybrid dye, the naphthyl and pyrenyl acetylenes do not form aggregates. In the aggregate state of the hybrid fluorophore, electronic energy transfer takes place from the naphthyl moiety to pyrenyl ring. The excited-state photophysical properties of the dye are exploited in vapor sensing in the solid state.
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    Newly Designed Resorcinolate Binding for Ru(II)– and Re(I)–Polypyridyl Complexes on Oleic Acid Capped TiO2 in Nonaqueous Solvent: Prolonged Charge Separation and Substantial Thermalized 3MLCT Injection
    (ACS, 2013-01-23) Banerjee, Tanmay
    Femtosecond pump–probe spectroscopic studies on a series of newly synthesized resorcinol-based Ru(II) and Re(I) complexes on oleic acid capped TiO2 nanoparticles have been carried out in chloroform, and the results are compared with those of the catechol analogues. The ruthenium complex shows biexponential injection; the second component arises due to injection from the thermally equilibrated 3MLCT states as a result of a weaker strength of the resorcinolate binding. Also, in comparison with catechol binding, as a result of a greater diffusion of the injected electrons into TiO2, the back electron transfer (BET) is slowed down significantly for the ruthenium complex. These are distinctive observations for any mononuclear ruthenium–polypyridyl–enediol complex reported thus far. However, the rhenium complex educes single exponential ultrafast injection (<120 fs) because of apparent injection in a high density of states and shows the most prominent results with ∼50% slowdown in the charge recombination rate as compared to the analogous catechol bound system. These results exemplify the probable development of highly capable sensitizer dyes with resorcinol as the anchoring group for the development of efficient dye-sensitized solar cells.
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    Traceless Directing Groups in Radical Cascades: From Oligoalkynes to Fused Helicenes without Tethered Initiators
    (ACS, 2014-12-24) Banerjee, Tanmay
    We report the first example of a traceless directing group in a radical cascade. The chemo- and regioselectivity of the initial attack in skipped oligoalkynes is controlled by propargyl OR moiety. Radical translocations lead to the boomerang return of the radical center to the site of initial attack where it assists the elimination of the directing functionality via β-scission in the last step of the cascade. The Bu3Sn moiety continues further via facile reactions with electrophiles as well as Stille and Suzuki cross-coupling reactions. This selective radical transformation opens a new approach for the controlled transformation of skipped oligoalkynes into polycyclic ribbons of tunable dimensions.
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    Alkenes as Alkyne Equivalents in Radical Cascades Terminated by Fragmentations: Overcoming Stereoelectronic Restrictions on Ring Expansions for the Preparation of Expanded Polyaromatics
    (ACS, 2015-04-23) Banerjee, Tanmay
    Chemoselective interaction of aromatic enynes with Bu3Sn radicals can be harnessed for selective cascade transformations, yielding either Sn-substituted naphthalenes or Sn-indenes. Depending on the substitution at the alkene terminus, the initial regioselective 5-exo-trig cyclizations can be intercepted at the 5-exo stage via either hydrogen atom abstraction or C–S bond scission or allowed to proceed further to the formal 6-endo products via homoallylic ring expansion. Aromatization of the latter occurs via β-C–C bond scission, which is facilitated by 2c,3e through-bond interactions, a new stereoelectronic effect in radical chemistry. The combination of formal 6-endo-trig cyclization with stereoelectronically optimized fragmentation allows the use of alkenes as synthetic equivalents of alkynes and opens a convenient route to α-Sn-substituted naphthalenes, a unique launching platform for the preparation of extended polyaromatics.
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    Protonated Benzene Dimer: An Experimental and Ab Initio Study
    (ACS, 2009-07-21) Chakraborty, Shamik
    The excitation spectrum of the protonated benzene dimer has been recorded in the 415−600 nm wavelength range. In contrast to the neutral iso-electronic benzene dimer, its absorption spectrum extends in the visible spectral region. This huge spectral shift has been interpreted with ab initio calculations, which indicate that the first excited states should be charge transfer states.
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    Gas-Phase Spectroscopy of Synephrine by Laser Desorption Supersonic Jet Technique
    (ACS, 2011-08-06) Chakraborty, Shamik
    In our previous work, we found that synephrine has six conformers in the gas phase, while adrenaline, which is a catecholamine and has the same side chain as synephrine, has been reported to have only two conformers. To determine the conformational geometries of synephrine, we measured resonance enhanced multiphoton ionization, ultraviolet–ultraviolet hole burning, and infrared dip spectra by utilizing the laser desorption supersonic jet technique. By comparing the observed infrared spectra with theoretical ones, we assigned geometries except for the orientations of the phenolic OH group. Comparison between the determined structures of synephrine and those of 2-methylaminno-1-phenylethanol, which has the same side chain as synephrine but no phenol OH group, leads to the conclusion that the phenolic OH group in synephrine does not affect the conformational flexibility of the side chain. In the case of adrenaline, which is expected to have 12 conformers if there are no interactions between the catecholic OH groups and the side chain, some interactions possibly exist between them because only two conformations are observed. By estimation of the dipole–dipole interaction energy between partial dipole moments of the catecholic OH groups and the side chain, it was concluded that the dipole–dipole interaction stabilizes specific conformers which are actually observed.