Reactions of carbamoylated amino enones with 3-substituted chromones for the preparation of 2-pyridones and chromeno[4,3-b]pyridine-2,5-diones

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Catalyst-Free Arylation of Tertiary Phosphines with Diaryliodonium Salts Enabled by Visible Light

The visible-light-induced arylation of tertiary phosphines with aryl(mesityl)iodonium triflates to produce the quaternary phosphonium salts occurs under mild, metal, and catalyst-free conditions. Photo-excited EDA complexes between diaryliodonium salts and phosphines supposedly enable this transformation, which is difficult to achieve through the traditional ground-state reactions. Demonstrating high functional group tolerance, broad scope, and complete selectivity of the aryl group transfer, the method is particularly compatible with sterically congested phosphines, which are challenging under metal-based catalytic methods.     

Furanose Bicyclophosphites as Synthons of Modified Nucleoside Diphosphates

Abstract

Previously we synthesized and examined in detail 1,2- alkylideneglucofuanose 3,5,6-bicyclophosphites; mono- and bicyclophosphates with peculiar chemical and physiological activity were obtained on their base [1]. During the study of their structural dependence, we modified the hydrocarbonic moiety, synthesiz-ed 1,2,3- and 3,5,6-bicyclophosphites and cyclophosphates of gulofuanose, and correlated their features with those of glucose analogues. Furthermore, an additional phosphonate moiety (obtained by a stereoselective reaction of an appropriate ketonic sugar with silylphosphites) was introduced into the glucofuranose 3,5,6-bicyclophosphite molecule to the third carbon atom. As a result, the monosaccharide matrix gained two functional groups containing tri- and fourcoordinated phosphorus.     

Non-Racemic Mixtures of 1,3,2-Oxazaphosphacyclanes - Enantiomeric Composition Determination by NMR

Abstract

The enantiomeric ratio in non-racemic mixtures of 2-anilino-2-oxo-1,3,2-oxazaphospho-rinane (I) and 3-(α-rnethylbenzyl)-(I)¹ enantiomers was determined by measurement of the integral intensity ratio of two ³¹P-NMR signals, assigned to enantiomers and differentiated due to the effect of statistically controlled associate-diastereoisomerim (scada), ² when association occurs under conditions of fast exchange.     

An efficient synthesis of new polyfunctional hexahydro pyrido[1,2-a]pyrazin-1-ones

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Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents

Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield Φ_T=60 %) was observed, with a triplet state lifetime (τ_T=436 μs) much longer than that accessed with the conventional heavy atom effect (τ_T=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the ¹CT/³LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC₅₀=75 nm ), with a negligible dark toxicity (EC₅₀=78.1 μm ) compared with the conventional heavy atom PSs (dark toxicity, EC₅₀=6.0 μm, light toxicity, EC₅₀=4.0 nm ). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.     

Pericyclic reactions in the synthesis of new 5-aryl-5,6-dihydroquinolino[2,1-b]quinazolin-12-ones

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