90367-83-2

Upstream product

• 100-42-5 styrene 
• 75-65-0 tert-butyl alcohol 
• 98946-18-0 tert-Butyl 2,2,2-trichloroacetimidate 
• 98-85-1 1-Phenylethanol 
• 100-41-4 ethylbenzene 
• 2324-98-3 2,3,5,6-tetrafluoroanisole 
• 865-48-5 sodium t-butanolate 
• 585-71-7 (1-bromoethyl)benzne 

Downstream Products

• 98-86-2 acetophenone 

Relevant academic research and scientific papers

Copper-Catalyzed Direct C-H Alkylation of Polyfluoroarenes by Using Hydrocarbons as an Alkylating Source

Construction of carbon-carbon bonds is one of the most important tools in chemical synthesis. In the previously established cross-coupling reactions, prefunctionalized starting materials were usually employed in the form of aryl or alkyl (pseudo)halides or their metalated derivatives. However, the direct use of arenes and alkanes via a 2-fold oxidative C-H bond activation strategy to access chemoselective C(sp2)-C(sp3) cross-couplings is highly challenging due to the low reactivity of carbon-hydrogen (C-H) bonds and the difficulty in suppressing side reactions such as homocouplings. Herein, we present the new development of a copper-catalyzed cross-dehydrogenative coupling of polyfluoroarenes with alkanes under mild conditions. Relatively weak sp3 C-H bonds at the benzylic or allylic positions, and nonactivated hydrocarbons could be alkylated by the newly developed catalyst system. A moderate-to-high site selectivity was observed among various C-H bonds present in hydrocarbon reactants, including gaseous feedstocks and complex molecules. Mechanistic information was obtained by performing combined experimental and computational studies to reveal that the copper catalyst plays a dual role in activating both alkane sp3 C-H bonds and sp2 polyfluoroarene C-H bonds. It was also suggested that the noncovalent π-πinteraction and weak hydrogen bonds formed in situ between the optimal ligand and arene substrates are key to facilitating the current coupling reactions.

Acid- and isobutylene-free synthesis of t-butyl ethers by in situ formation of 2-t-butoxy-1-methylpyridinium triflate

The title reagent is formed in situ by alkylation of 2-t-butoxypyrine. The subsequent addition of an alcohol substrate leads to the formation of t-butyl ethers without the need for isobutylene gas or acid activators.

Hydroalkoxylation of unactivated olefins with carbon radicals and carbocation species as key intermediates

A unique Markovnikov hydroalkoxylation of unactivated olefins with a cobalt complex, silane, and N-fluoropyridinium salt is reported. Further optimization of reaction conditions yielded high functional group tolerance and versatility of alcoholic solvent employed, including methanol, i-propanol, and t-butanol. Use of trifluorotoluene as a solvent made the use of alcohol in stoichiometric amount possible. Mechanistic insight into this novel catalytic system is also discussed. Experimental results suggest that catalysis involves both carbon radical and carbocation intermediates.

CATALYTIC C-H BOND ACTIVATION FOR THE SYNTHESIS OF ETHERS AND THIOETHERS

Disclosed is a method for the transition metal-mediated oxidation of C-H bonds to form C-0 or C-S bonds. The methods are useful for the formation of ethers (R-OR') from alcohols, R'OH, and sp3 -hybridized C-H bonds in substrates, R-H. Aryl or heteroaryl acetates may also be used for C-H to C-OAr bond formation. The methods are also useful in the preparation of C-S bonds from acetyl-protected thiols, MeC(0)SR, and disulfides, RSSR. Advantageously, the methods minimize reaction steps, the handling of oxidized intermediates, and environmental impact.

Catalytic hydroalkoxylation of alkenes by iron(III) catalyst

Catalytic hydroalkoxylation of alkenes by iron(III) chloride in the presence of toluenesulfonic acid (TsOH) was developed in moderate to good yields up to 91%. Intramolecular cyclization of 5-hydroxyl pentene afforded 2-methyltetrahedronfuran in 63% yield.

BiBr3, an efficient catalyst for the benzylation of alcohols: 2-Phenyl- 2-propyl, a new benzyl-type protecting group

The benzylation of aliphatic alcohols with various benzylic alcohols has been achieved in the presence of BiBr3 under mild conditions. 2- Phenylpropan-2-ol proved to be the most efficient and can be considered as a novel protecting group. (C) 2000 Elsevier Science Ltd.

ENHANCED NUCLEOPHILE SELECTIVITY IN THE PHOTOADDITION TO STYRENE. COMPARISON WITH THE THERMAL ADDITION

The reactivity-selectivity properties of the sec-phenethyl carbenium ion and its analogues have been examined in binary-aqueous solutions of alcohols (ROH; R = Me, Et, CF3CH2, n-Bu, t-Bu, n-Pr, i-Pr), acetic acid, and in solutions containig external nucleophiles such as thiophenol, ethanethiol, acetate, and benzenesulfinate.Selectivity (S = k(Nuc)/k(H2O) is observed to be a function of the nucleophile, the ring substituent, thermal or photochemical conditions, irradiation time, and medium acidity.In the case of styrene, the photochemically generated (usually 254 nm, 1 h) species exhibits greater selectivity (up to two orders of magnitude) than its thermal counterpart, generated (usually 80 deg C, 2-4 d) in identical media, particularly in aqueous-rich solvent compositions.A rationale for these differences, supported by fluorescence quenching experiments, and the other effects upon selectivity will be discussed.

A NEW METHOD FOR THE PREPARATION OF TERTIARY BUTYL ETHERS AND ESTERS

T-butyl 2,2,2-trichloroacetimidate (1), readily prepared by addition of t-butanol to trichloroacetonitrile, is an efficient reagent for the preparation of t-butyl ethers and esters in the presence of a catalytic amount of boron trifluoride etherate.

Solvomercuration-Demercuration. 12. The Solvomercuration-Demercuration of Olefins in Alcohol Solvents with Mercuric Trifluoroacetate--An Ether Synthesis of Wide Generality

Studies on the solvomercuration-demercuration (SM-DM) of olefins in methyl, ethyl, isopropyl, and tert-butyl alcohols with mercuric trifluoroacetate have been extended. 1-Dodecene undergoes the SM-DM sequence with typical results for a monosubstituted olefin.Cyclopentene similarly exhibited behavior characteristic of a 1,2-disubstituted olefin in methanol, ethanol, and 2-propanol, giving high yields, >90percent of the corresponding ethers.However, in tert-butyl alcohol, the yields of ether were lower than normal and decreased somewhat with time. 2-Methyl-1-butene gives >90percent yields of the Markovnikov methyl ether.On the other hand, the yields of ethyl, isopropyl, and tert-butyl ethers are lower and decrease with time.Major improvements in yields, however, are possible by lowering the reaction temperature from room temperature to 0 deg C.Cyclooctene, surprisingly, behaves more like a tri-, tetra-, or isosubstituted olefin than a 1,2-disubstituted olefin.The yields of cyclooctyl methyl ether are >90percent and do not decrease with time.However, yields of the ethyl, isopropyl, and tert-butyl ethers are lower and drop with time.Again, lowering the reaction temperature from room temperature to 0 deg C markedly improves the yields of the cyclooctyl ethers.These results, coupled with those of a previous study, clearly reveal the exceptional superiority of mercuric trifluoroacetate for the SM-DM of olefins in alcohol solvents.