02274nas a2200205 4500008004100000022001400041245012100055210006900176260000900245300000800254490000700262520153100269100002301800700002501823700002101848700003001869700001701899700002201916856013001938 2022 eng d a0039-788100aEnantioselective Cu(I)-catalyzed borylative cyclization of enone-tethered cyclohexadienones and mechanistic insights0 aEnantioselective CuIcatalyzed borylative cyclization of enonetet cFEB  a8540 v133 a

Rapidly building molecular structures with both elements of complexity and flexibility is a key goal of organic synthesis. Here the authors show a tandem copper-catalyzed beta-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones, to generate bicyclic borylated products in high yield and enantioselectivity. The catalytic asymmetric borylation of conjugated carbonyls followed by stereoselective intramolecular cascade cyclizations with in situ generated chiral enolates are extremely rare. Herein, we report the enantioselective Cu(I)-catalyzed beta-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones. This asymmetric desymmetrization strategy has a broad range of substrate scope to generate densely functionalized bicyclic enones bearing four contiguous stereocenters with excellent yield, enantioselectivity, and diastereoselectivity. One-pot borylation/cyclization/oxidation via the sequential addition of sodium perborate reagent affords the corresponding alcohols without affecting yield and enantioselectivity. The synthetic potential of this reaction is explored through gram-scale reactions and further chemoselective transformations on products. DFT calculations explain the requirement of the base in an equimolar ratio in the reaction, as it leads to the formation of a lithium-enolate complex to undergo C-C bond formation via a chair-like transition state, with a barrier that is 22.5 kcal/mol more favourable than that of the copper-enolate complex.

1 aJadhav, Sandip, B.1 aDash, Soumya, Ranjan1 aMaurya, Sundaram1 aNanubolu, Jagadeesh, Babu1 aVanka, Kumar1 aChegondi, Rambabu uhttps://library.ncl.res.in/content/enantioselective-cui-catalyzed-borylative-cyclization-enone-tethered-cyclohexadienones-and01858nas a2200265 4500008004100000022001400041245009300055210006900148260000800217300001500225490000700240520100900247653002401256653002401280653000801304653002701312653001801339100001701357700002501374700001601399700001701415700001701432700001901449856012401468 2023 eng d a2192-650600aEnhancing diradical character of chichibabin's hydrocarbon through fluoride substitution0 aEnhancing diradical character of chichibabins hydrocarbon throug cAUG ae2023002730 v883 a

In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin's hydrocarbon with an octafluorobiphenylene spacer (3) has been reported. The addition of two equivalents of 5-SIDipp with decafluorobiphenyl in presence of BF3 gives the double C-F bond activated imidazolium salt with two tetrafluoroborate anions, 2. Further reduction of 2 gives the fluorine substituted 5-SIDipp based Chichibabin's hydrocarbon, 3. Quantum chemical calculations suggested a singlet state of 3 with a singlet-triplet energy gap (?ES-T) of 3.7 kcal mol(-1), which is substantially lower with respect to the hydrogen substituted NHC-based Chichibabin's hydrocarbons (10.7 kcal mol(-1), B3LYP). As a result, the diradical character (y) of 3 (y=0.62) is also noticeably higher than the hydrogen substituted CHs (y=0.41-0.43). The ?ES-T was found to be higher in CASSCF (22.24 kcal mol(-1)) and CASPT2 (11.17 kcal mol(-1)) for 3 and the diradical character (d) is 44.6 %.

10aC-F Bond Activation10aChichibabin & PRIME10aDFT10aN-Heterocyclic carbene10as Hydrocarbon1 aKundu, Gargi1 aDash, Soumya, Ranjan1 aKumar, Ravi1 aVanka, Kumar1 aGhosh, Aryya1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/enhancing-diradical-character-chichibabins-hydrocarbon-through-fluoride-substitution02184nas a2200205 4500008004100000022001400041245014300055210007000198260000800268490000700276520142000283653002001703653002601723653003001749653001501779653000901794100002501803700001701828856013301845 2024 eng d a1439-423500aExploring unconventional σ-hole interactions: computational insights into the interaction of XeO3 with non-aromatic coordinating solvents0 aExploring unconventional σhole interactions computational insigh cMAR0 v253 a

In order to control the explosiveness and shock sensitivity of XeO3, we have investigated its plausible interaction with various non-aromatic coordinating solvents, serving as potential Lewis base donors, through density functional theory (DFT) calculations. Out of twenty six such solvents, the top ten were thus identified and then thoroughly examined by employing various computational tools such as the mapping of the electrostatic potential surface (MESP), Wiberg bond indices (WBIs), non-covalent interaction (NCI) plots, Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, and the energy decomposition analysis (EDA). The amphoteric nature of XeO3 was also explored by investigating the extent of back donation from the lone pair of Xe to the antibonding orbital of the donating atom/group of the solvent molecules. The C-H & mldr;O interactions were also found to be a contributing factor in the stabilization of these adducts. Although these aerogen-bonding interactions were found to be predominantly electrostatic, significant contributions from the orbital contributions, as well as dispersion interactions, were observed. The top three non-aromatic solvents (among the twenty six studied) which form the strongest adducts with XeO3 are proposed to be hexamethylphosphoramide (HMPA), N,N `-dimethylpropyleneurea (DMPU) and tetramethylethylenediamine (TMEDA).

10aAerogen bonding10aNon-Aromatic Solvents10anon-covalent interactions10aSigma-hole10aXeO31 aDash, Soumya, Ranjan1 aVanka, Kumar uhttps://library.ncl.res.in/content/exploring-unconventional-%CF%83-hole-interactions-computational-insights-interaction-xeo3-non