ABSTRACT
A facile and mild Ru(II)-catalyzed ortho-C-H hydroxyfluoroalkylation of arenes with cheap and easily accessible fluorinated alcohols has been developed in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The readily available fluorinated alcohols were used as hydroxyfluoroalkylation reagents to form various α-aryl-α-trifluoromethyl alcohols. The present work provides a new method for the introduction of hydroxyfluoroalkyl groups into arenes.
ABSTRACT
An original and facile method for the generation of ß-naphtha-1-thioquinones using DAST and 2-naphthols has been developed. A series of dehydro-2-naphthol-1-sulphides or naphtha-oxathiane derivatives were synthesized by in situ Diels-Alder cycloaddition reactions of ß-naphtha-1-thioquinone with itself or various alkenes.
Subject(s)
Naphthols , Alkanes , Cycloaddition Reaction , Diethylamines , Fluorine , Solvents , StereoisomerismABSTRACT
A mild and efficient Cu-assisted trifluoromethylthiolation/radical cascade cyclization of alkynes with readily available and stable AgSCF3 as the trifluoromethylthiolating reagent has been disclosed. This transformation provides an opportunity to construct a series of potential medicinally valuable trifluoromethylthio-substituted dioxodibenzothiazepines with wide functional group compatibility. This protocol opens up a new avenue for the construction of useful trifluoromethylthiolated seven-membered N-heterocycles.
Subject(s)
Alkynes , Copper , Catalysis , Cyclization , Indicators and ReagentsABSTRACT
An efficient copper-catalyzed cascade difunctionalization of N-allyl anilines toward the synthesis of silylated indolines using commercially available silanes has been reported. This strategy provides a new avenue for the synthesis of a diverse array of indolines in reasonable yields. Preliminary mechanistic investigations indicate that the reaction probably proceeds via a radical pathway with unactivated alkenes as radical acceptors and simple silanes as radical precursors. This protocol is distinguished by its atom economy, broad substrate scope and readily available starting materials.
ABSTRACT
The first metal-free method for alkylation of quinoxalinones using cheap and stable aryl alkyl ketones as nucleophilic alkylation reagents is reported. This strategy greatly broadens the application channels of aryl alkyl ketones through carbon-carbon bond activation. In addition, the protocol has the advantages of simple operation, broad substrate scope, and good functional group tolerance.
ABSTRACT
A mild and efficient visible-light-induced radical difluoromethylation/cyclization of unactivated alkenes toward the synthesis of substituted quinazolinones with easily accessible difluoromethyltriphenylphosphonium bromide has been developed. The transformation has the advantages of wide functional group compatibility, a broad substrate scope, and operational simplicity. The benign protocol offers a facile access to pharmaceutically valuable difluoromethylated polycyclic quinazolinones.
ABSTRACT
Herein, we developed the first visible-light-induced direct Csp2-H radical 2,2,2-trifluoroethylation of coumarins with commercially available and cheap reagent CF3CH2I at room temperature. This transformation proceeded smoothly under mild conditions and showed excellent functional group compatibility. The synthetic value of the protocol was also demonstrated by the successful functionalization of several pharmaceuticals.
Subject(s)
Coumarins , Light , Hydrocarbons, HalogenatedABSTRACT
Here, complex 1 ([Ru(bpy)2(hpip)]2+-MV2+) and CB[8] can form a stable 1 : 1 inclusion complex in aqueous solution, resembling a U-shaped conformation. Upon light irradiation, two complex 1 were reversibly locked through the formation of a MVË+ radical dimer that is stabilized in the cavity of CB[8] with Ru complexes as blockers, in which complex 1 was transformed from a U-shaped conformation to a interlocked complex. This study provided a feasible strategy for the fabrication of a photo-driven supramolecular machine resembling a "lock".
ABSTRACT
A novel and efficient method for the generation of alkyl radicals and the alkylation of quinoline and pyridine derivatives under mild conditions has been developed. This strategy allows the direct alkylation of heteroaromatics in the absence of an external oxidant. A preliminary mechanistic study suggests that the present reaction probably proceeds via an intermolecular HAT process.
ABSTRACT
The first palladium-catalyzed Hiyama cross-coupling reactions of arylsilanes with 3-iodoazetidine were described. The protocol provides a convenient access to a variety of useful 3-arylazetidines which are of great interest in pharmaceutical laboratories in moderate to good yields (30%-88%). In addition, this strategy has the advantage of easy operation and mild reaction conditions.
ABSTRACT
A novel oxidation of benzylic C-H bonds for the synthesis of diverse six-membered N-heteroaromatic aldehydes and ketones has been developed. The obvious advantages of this approach are the simple operation, mild reaction conditions, and without use of toxic reagent and transition metal. The present method should provide a useful access for the synthesis and modification of N-heterocycles.
ABSTRACT
Herein, a novel quinoline-based fluorescent probe DQPH has been developed for ratiometric detection of subtle pH fluctuation in biosystem. Upon altering the pH from 4.50 to 9.00, the emission spectra exhibit a large hypsochromic shift (57â¯nm) and the ratio of fluorescence intensity (F531â¯nm/F588â¯nm) changes from 0.30 to 1.36 with an ideal pKa value of 7.18 and a linear pH variation range of 6.35-8.00. The ratiometric response is attributed to the protonation-activable resonance charge transfer (PARCT) process, which has been proved by 1H NMR and NOESY experiment. This probe displayed good solubility, low cytotoxicity, anti-interference capability and reversible pH sensing. Furthermore, DQPH was successfully applied for monitoring pH changes in living cells.
Subject(s)
Fluorescent Dyes/chemistry , Quinolines/chemistry , Animals , Cells, Cultured , Fluorescence , Hydrogen-Ion Concentration , Mice , Microscopy, Confocal , Molecular Structure , NIH 3T3 Cells , Solutions , Water/chemistryABSTRACT
The first Pd-catalyzed alkylation of (iso)quinolines and arenes is reported. The readily available and bench-stable 2-acylpyridine compounds were used as an alkylation reagent to form the structurally versatile alkylated (iso)quinolines and arenes. The method affords a convenient pathway for the introduction of alkyl groups into organic molecules.
ABSTRACT
An efficient nickel-catalyzed C-H trifluoromethylation for the synthesis of trifluoromethylated free anilines using Togni's reagent has been developed. This approach exhibits a good functional group tolerance, good regioselectivity, and chemoselectivity under mild conditions. The newly developed economical one-step method is a better alternative to synthesize trifluoromethylated free anilines.
ABSTRACT
The first O-difluorodeuteromethylation of phenols using commercial diethyl bromodifluoromethylphosphonate and deuterium oxide to prepare various difluorodeuteromethyl aryl ethers is reported. This facile method affords a convenient way to introduce OCF2D groups into organic molecules.
ABSTRACT
A new on-off-on fluorescent probe, CMOS, based on coumarin was developed to detect the process of hypochlorous acid (HOCl) oxidative stress and cysteine/homocysteine (Cys/Hcy) reduction. The probe exhibited a fast response, good sensitivity and selectivity. Moreover, it was applied for monitoring the redox process in living cells.
ABSTRACT
The first palladium-catalyzed diastereoselective conjugate addition of arylboronic acids to chiral imides is reported. The catalytic system employing 4-tert-butyloxazolidin-2-one as the chiral auxiliary in a mixed solvent system of MeOH/H2O (1:3) under an air atmosphere provides the optically active 3-arylbutanoic acid derivatives in excellent yields with high diastereoselectivity.
ABSTRACT
An efficient CuI-catalyzed fluorodesulfurization for the synthesis of monofluoromethyl aryl ethers using DAST at room temperature has been developed. This approach exhibits a good functional group tolerance, a broad substrate scope, and a high synthesis efficiency.
ABSTRACT
The first Pd-catalyzed tandem cyclization of imidazo[1,2-a]pyridines with 2-chlorobenzaldehydes through C-H arylation and acylation is presented for the efficient synthesis of novel 6H-benzo[b]imidazo[5,1,2-de]quinolizin-6-ones. The direct acylation reaction proceeded smoothly without the aid of directing groups and in the presence of air as a clean and free terminal oxidant.
ABSTRACT
A metal-free reduction of aromatic nitro compounds to the corresponding amines has been achieved by a combination of B2pin2 and KOtBu in isopropanol. A series of nitro compounds containing various reducible functional groups were chemoselectively reduced in good to excellent yields.