4747-11-9

Usage

InChI:InChI=1/C14H14O/c1-12(13-8-4-2-5-9-13)15-14-10-6-3-7-11-14/h2-12H,1H3

Upstream product

• 585-71-7 (1-bromoethyl)benzne 
• 108-95-2 phenol 
• 3886-69-9 (R)-1-phenyl-ethyl-amine 
• 98-85-1 1-Phenylethanol 
• 6840-01-3 (dimethylamino)(diphenyl)phosphine 
• 134920-71-1 1-Diphenylphosphinoxy-1-phenylethan 
• 1053188-61-6 1-iodo-2-(1-phenylethoxy)benzene 
• 100-42-5 styrene 
• 14531-53-4 methyl cation 
• 946-80-5 (benzyloxy)benzene 
• 5661-68-7 1,1'-diphenylazoethane 
• 31575-75-4 2-bromophenyl benzyl ether 
• 74-88-4 methyl iodide 
• 100-39-0 benzyl bromide 

Downstream Products

• 40391-43-3 (E)-1,4-diphenylpent-1-en-3-ol 
• 100-42-5 styrene 
• 108-95-2 phenol 
• 98-85-1 1-Phenylethanol 
• 23637-42-5 (1E,3E)-1,4-diphenyl-1-methyl-1,3-butadiene 
• 40391-41-1 (1Z,3E)-1,4-diphenyl-1-methyl-1,3-butadiene 
• 4237-44-9 2-(1-phenylethyl)phenol 
• 120346-43-2 1-(4-hydroxyphenyl)-1-phenylethane 

Relevant academic research and scientific papers

Iodine catalysed synthesis of unsymmetrical benzylic ethers by direct cross-coupling of alcohols

Although symmetrical ethers can be synthesized easily from alcohols, synthesis of unsymmetrical ethers by dehydrative cross-coupling of alcohols is still a challenge. While dehydrative cross-coupling is environmentally appealing due to formation of water as the only byproduct, the chances for formation of symmetrical ethers always exist. The existing transition metal based methods give good selectivity, but the catalyst are costly and not readily available. Here, we present a simple, readily available, and cost-effective catalyst in the form of molecular iodine which catalyzes a highly selective cross-coupling of benzylic alcohols with benzyl, alkyl, and aryl alcohols to give their corresponding unsymmetrical ethers in good to excellent yield.

Radical Capture at Nickel(II) Complexes: C-C, C-N, and C-O Bond Formation

The dinuclear β-diketiminato NiII tert-butoxide {[Me3NN]Ni}2(μ-OtBu)2 (2), synthesized from [Me3NN]Ni(2,4-lutidine) (1) and di-tert-butylperoxide, is a versatile precursor for the synthesis of a series of NiII complexes [Me3NN]Ni-FG (FG = functional group) to illustrate C-C, C-N, and C-O bond formation at NiII via radical capture. {[Me3NN]Ni}2(μ-OtBu)2 reacts with nitromethane, alkyl and aryl amines, acetophenone, benzamide, ammonia, and phenols to deliver the corresponding mono- or dinuclear [Me3NN]Ni-FG species (FG = O2NCH2, R-NH, ArNH, PhC(O)NH, PhC(O)CH2, NH2, and OAr). Many of these NiII complexes are capable of capturing the benzylic radical PhCH(?)CH3 to deliver the corresponding PhCH(FG)CH3 products featuring C-C, C-N, or C-O bonds. Density functional theory studies shed light on the mechanism of these transformations and suggest two competing pathways that depend on the nature of the functional groups. These radical capture reactions at [NiII]-FG complexes outline key C-C, C-N, and C-O bond forming steps, foreshadowing families of nickel radical relay catalysts.

α-Lithiobenzyloxy as a Directed Metalation Group in ortho-Lithiation Reactions

The α-lithiobenzyloxy group, easily generated from aryl benzyl ethers by selective α-lithiation with t-BuLi at low temperature, behaves as a directed metalation group (DMG) providing a direct access to o-lithiophenyl α-lithiobenzyl ethers. This ortho-directing effect is reinforced in substrates bearing an additional methoxy group at the meta position. The generated dianions can be reacted with a selection of electrophiles including carboxylic esters and dihalosilanes or germanes, which afford interesting benzofuran, sila(germa)dihydrobenzofuran, and silachroman derivatives from simple aryl benzyl ethers.

Control of tandem isomerizations: Flow-assisted reactions of: O -lithiated aryl benzyl ethers

Tandem chemical changes are often difficult to control at will, because they proceed rapidly through multiple unstable reactive intermediates. It is desirable to develop a novel method for controlling such tandem changes to obtain desired products with high selectivity. Herein, we report a flow microreactor platform for controlling tandem isomerizations of o-lithiated aryl benzyl ethers based on precise residence time control.

Copper Catalyzed sp3 C-H Etherification with Acyl Protected Phenols

A variety of acyl protected phenols AcOAr participate in sp3 C-H etherification of substrates R-H to give alkyl aryl ethers R-OAr employing tBuOOtBu as oxidant with copper(I) β-diketiminato catalysts [CuI]. Although 1°, 2°, and 3° C-H bonds may be functionalized, selectivity studies reveal a preference for the construction of hindered, 3° C-OAr bonds. Mechanistic studies indicate that β-diketiminato copper(II) phenolates [CuII]-OAr play a key role in this C-O bond forming reaction, formed via transesterification of AcOAr with [CuII]-OtBu intermediates generated upon reaction of [CuI] with tBuOOtBu.

Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited

By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α-lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]-Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α-lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron-poor aryl groups that favor the anionic pathway.

Synthesis and catalytic activity of monobridged bis(cyclopentadienyl)rhenium carbonyl complexes

Thermal treatment of three monobridged biscyclopentadienes (C5H5)R(C5H5) [R?=?C(CH3)2 (1), C(CH2)5 (2), Si(CH3)2 (3)] with Re2(CO)10 in refluxing mesitylene gave the corresponding complexes [(η5-C5H4)2R][Re(CO)3]2 [R?=?C(CH3)2 (4), C(C5H10) (5), Si(CH3)2 (6)], which were separated by chromatography, and characterized by elemental analysis, IR, and 1H NMR spectroscopy. The molecular structures of complexes 5 and 6 were characterized by X-ray crystal diffraction analysis and show that both are monobridged bis(cyclopentadienyl)rhenium carbonyl complexes in which the molecule consists of two [(η5-C5H4)Re(CO)3] moieties linked by a single bridge, in which each of the two Re(CO)3 units is coordinated to the cyclopentadienyl ring in an η5 mode. All three of these monobridged bis(cyclopentadienyl)rhenium carbonyl complexes have good catalytic activities in Friedel–Crafts alkylation reactions.

From insertion to multicomponent coupling: Temperature dependent reactions of arynes with aliphatic alcohols

The temperature dependent selectivity switch in the reaction of arynes with aliphatic alcohols in THF has been reported. At -20°C, arynes smoothly insert into the O-H bond of alcohols to form alkyl aryl ethers. Interestingly, at 60°C, a highly selective multicomponent coupling occurs with the solvent THF acting as the nucleophilic trigger affording (4-(alkoxy)butoxy)arenes.

α-Lithiated Aryl Benzyl Ethers: Inhibition of [1,2]-Wittig Rearrangement and Application to the Synthesis of Benzo[b]furan Derivatives

The use of t-BuLi at low temperature selectively leads to α-lithiation of benzyl phenyl ether generating a stable organolithium, which can be efficiently trapped with a variety of selected electrophiles prior to suffering the expected [1,2]-Wittig rearrangement. In the case of (o-alkynyl)phenyl benzyl ethers, the intermediate α-aryloxyorganolithium undergoes an unexpected anti intramolecular carbolithiation reaction leading to functionalized benzo[b]furan derivatives.

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.