Crucial dependence of chemiluminescence efficiency on the syn/anti conformation for intramolecular charge-transfer-induced decomposition of bicyclic dioxetanes bearing an oxidoaryl group

Thermally stable rotamers of bicyclic dioxetanes bearing 6-hydroxynaphthalen-1-yl (anti-5a and syn-5a), 3-hydroxynaphthalen-1-yl (anti-5b and syn-5b), and 5-hydroxy-2-methylphenyl groups (anti-5c and syn-5c) were synthesized. These dioxetanes underwent TBAF (tetrabutylammonium fluoride)-induced decomposition accompanied by the emission of light in DMSO and in acetonitrile at 25 °C. For all three pairs of rotamers, the chemiluminescence efficiency Φ(CL) for anti-5 was 8-19 times higher than that for syn-5, and the rate of CTID (charge-transfer-induced decomposition) for anti-5 was faster than that for syn-5. The chemiluminescence spectra of the rotamers for 5a and 5c, respectively, were different. This discrepancy in the chemiluminescence spectra between rotamers can presumably be attributed to the difference in the structures of de novo keto imide anti-14 and syn-14 in an excited state, which inherit the structures of the corresponding intermediary anionic dioxetanes anti-13 and syn-13. The important difference in chemiluminescence efficiency between anti-5 and syn-5 is discussed from the viewpoint of a chemiexcitation mechanism for CTID of oxidophenyl-substituted dioxetane.     

Analgesic Characteristics of NanoBEO Released by an Airless Dispenser for the Control of Agitation in Severe Dementia

Chronic pain is one of the most common causes of the need for clinical evaluation, acquiring more importance in the elderly with cognitive impairment. Reduced self-reporting capabilities cause unrelieved pain contributing to the development of agitation. Safe and effective pain treatment can afford the management of agitation without the serious increase in death risk associated with neuroleptics. To this aim, the essential oil of bergamot (BEO), proven by rigorous evidence to have strong preclinical anti-nociceptive and anti-allodynic properties, has been engineered (NanoBEO, patent EP 4003294) to allow randomized, double-blind, placebo-controlled trials (BRAINAID, {"type":"clinical-trial","attrs":{"text":"NCT04321889","term_id":"NCT04321889"}}NCT04321889). The present study: (1) assesses the analgesic effects of a single therapeutic dose of NanoBEO, as supplied by an airless dispenser for clinical translation, in models of inflammatory, neuropathic, and sensitization types of pain relevant to clinic; (2) provides a dose–response analysis of the efficacy of NanoBEO on scratching behavior, a typical behavioral disturbance occurring in dementia. A single therapeutic dose of NanoBEO confirms efficacy following thirty minutes pre-treatment with capsaicin and on the central sensitization phase induced by formalin. Moreover, it has an ID50 of 0.6312 mg and it is efficacious on static and dynamic mechanical allodynia. Altogether, the gathered results strengthen the potential of NanoBEO for clinical management of pain and agitation.     

Determination of enantiomeric purity of axially chiral biaryls

Enantiomeric purities of axially chiral biaryls with hydroxyl, amino, and carboxyl groups can be easily determined by pmr spectra using MTPA derivatives and shift reagent.     

Determination of absolute configuration of axially chiral biaryls

Absolute configurations of axially chiral biaryls with hydroxyl, amino, and carboxyl groups can be easily determined by pmr spectra using MTPA derivatives and shift reagents.     

A novel and efficient chiral palladium-phosphinooxazolidine catalyst for the enantioselective Diels-Alder reaction

An efficient ruthenium-catalyzed transfer dehydrogenation of amines to imines was acheived under mild conditions using 2,6-dimethoxy benzoquinone (2) or cat. 2/MnO2 as oxidant.     

Crystal and molecular structure of 9,10-diphenylbicyclo[6.2.0]decapentaene a 10 π aromatic compound

X-ray analysis of 9,10-diphenylbicyclo[6.2.0]decapentaene $\text{2b}$ has revealed good planarity of the decapentaene nucleus, remarkably long bond length of the central bond, and appreciably small alternation of the peripheral bonds. It is thus concluded that $\text{2b}$ is a pericyclic 10 π aromatic compound.     

eta1:eta2-Alkynyl-bridged W-Si complexes: formation, structure, and reaction with acetone

Reactions of (eta5-C5Me4R)(CO)2(MeCN)WMe (R = Me, Et) with HPh2SiCCtBu gave the novel alkynyl-bridged W-Si complexes, (eta5-C5Me4R)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) (R = Me, Et), whose alkynyl ligands bridge the tungsten and silicon atoms in an eta1:eta2-coordination mode. The structures of these complexes were fully characterized, including X-ray crystallography. Treatment of (eta5-C5Me5)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) with acetone resulted in acetone insertion into the silicon-alkynyl linkage followed by intramolecular C-H activation of the tBu group to give the chelate-type alkyl-alkene complex, (eta5-C5Me5)(CO)2W(eta1:eta2-CH2CMe2C=CHSiPh2OCMe2).     

Novel substituent effects on the mechanism of the thermal denitrogenation of 2,3-diazabicyclo[2.2.1]hept-2-ene derivatives, stepwise versus concerted

The substituent effect on the thermal denitrogenation mechanism of 7,7-disubstituted 2,3-diazabicyclo[2.2.1]hept-2-enes, concerted versus stepwise, has been investigated in detail. Unrestricted DFT calculations at the B3LYP/6-31G(d) level of theory suggest that azoalkanes that possess electron-withdrawing substituents at C(7) prefer to expel the nitrogen molecule in a stepwise manner. The activation energy is calculated to be ca. 36 kcal/mol for the dihydroxy-substituted azoalkane. In contrast, the preferred mechanism of the concerted denitrogenation is predicted for azoalkanes that possess electron-donating substituents at C(7). The activation energy is computed to be ca. 28 kcal/mol for the silyl-substituted azoalkane. The theoretical prediction of the substituent effects on the mechanistic change is supported by analyzing the activation parameters of the azoalkane decompositions. The activation enthalpy for the decomposition of the 7,7-diethoxy-substituted azoalkane is determined to be 39.1 kcal/mol, which is 13.1 kcal/mol higher in energy for the denitrogenation of the 7-silyl-substituted azoalkane. These dramatic substituent effects can be reasonably explained by the preferred electronic configuration of the lowest singlet state of the cyclopentane-1,3-diyls produced during the denitrogenation of the azoalkanes.     

Novel eta 3 -1-silaallyl tungsten complexes via Si-H bond activation of hydrovinylsilanes: structure and reactivity toward methanol

Reactions of cis-Cp*(CO)2W(MeCN)Me (1) with HSiMe2(CH=CR2) (R = H, Me) afford the novel eta3-1-silaallyl complexes Cp*(CO)2W(eta3-Me2SiCHCR2) [R = H (2), Me (3)] accompanied by liberation of MeCN and CH4 via thermal Si-H bond activation. eta3-Coordination and exo conformation of the 1-silaallyl ligand in 3 are shown by X-ray crystal analysis, which reveals the partial double bond character of the Si-C bond (1.800(4) A) in the silaallyl moiety. Complexes 2 and 3 show extremely high reactivity toward MeOH to give the hydrido-(methoxysilyl)alkene complex trans-Cp*(CO)2WH(eta2-MeOMe2SiCH=CH2) (4) and the four-membered metallacycle Cp*(CO)2WCH(CHMe2)SiMe2OMe (6), respectively.     

Use of Sm(III)-{1,2-propanediamine-N,N,N',N'-tetra(alpha,alpha-dideuterioacetate)} complex for NMR determination of absolute configuration of each alpha-amino acid in peptide hydrolysate mixtures

(1)H NMR analyses of individual alpha-amino acids in their mixture were simultaneously conducted in the presence of Sm-(pdta-d(8)) in water: high regularity, promising for direct simultaneous determination of absolute configurations of each alpha-amino acids in peptide hydrolysate mixtures, was observed between absolute configuration and the induced shifts.