Vinyl aryl ethers from copper-catalyzed coupling of vinyl halides and phenols

Cycloalkenyl Halide Substitution Reactions of Enantiopure Arene cis‐Tetrahydrodiols with Boron, Nitrogen and Phosphorus Nucleophiles

“…Similar reactions using copper catalysts are also gaining prominence [30] but the corresponding reactions with cycloalkenyl halides [31][32][33] or triflates, [34] or trifluoroborate salts [35] have not been as widely studied, possibly, because the reaction products are not as stable as in the aromatic series. Substitution of the bromine atom in compound 3d by a nitrogen atom (secondary amine) has the potential to give an enamine.…”

“…The crude product obtained after removal of the solvents was purified by PLC (EtOAc-hexane, 1:1) to give diol 2m as an oil, yield: 39 mg (85%); [a] D : À101 (c 0.3, MeOH), lit. [25] [a] D : À105 (c 0.8, MeOH); (30).…”

Organometallic Approaches to Carbon–Sulfur Bond Formation

“…Additional improvements continue to be made by modification of the reaction conditions, particularly the choice of ligand [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54]. Typically, conditions found to be successful for O-and N-arylation were tested in S-arylation.…”

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene

“…New methods of aryl vinyl ethers production are under development, among which the following are worth considering: catalytic reaction of phenols with various vinyl equivalents, e.g., vinyl halides [25, 26], vinylboronic acids [27, 28], tetravinyl-and tributyl-(vinyl)tin [29], vinyl esters of carboxylic acids [21, 30], and also the synthesis of aryl vinyl ethers from 2-phenylselenyl-ethanol [31-33] or 2-phenylsulfonylethanol [34] and phenols at treating with Mitsunobu reagent (diethyl ether of azodicarboxylic acidtriphenylphosphine). Recently a new two-stage method was patented of the production of aromatic vinyl ethers in a low yield (10-38%) involving vinylation of 2-aryloxyethanols (100 о С, 3-6 h, acetylene pressure 1.4 at, KОН-DMSO) with the formation of the corresponding 2-aryloxyethyl vinyl ethers followed by heating of the latter (130-140 о С, 6-10 h, DMSO) in the presence of double molar excess of KОН [35].The classic synthesis method of aryl vinyl ether through direct phenol vinylation with acetylene under the basic catalysis conditions not only conserves its importance but possesses obvious advantages before the mentioned procedures [21,[25][26][27][28][29][30][31][32][33][34][35] since it is atomeconomical, one-stage, and is based on a raw material of a large-scale production. Phenols add to acetylene in the presence of KОН at a high pressure (30-50 at) and a high temperature (180-200 о С) [2,[36][37][38][39][40].…”

“…The classic synthesis method of aryl vinyl ether through direct phenol vinylation with acetylene under the basic catalysis conditions not only conserves its importance but possesses obvious advantages before the mentioned procedures [21,[25][26][27][28][29][30][31][32][33][34][35] since it is atomeconomical, one-stage, and is based on a raw material of a large-scale production. Phenols add to acetylene in the presence of KОН at a high pressure (30-50 at) and a high temperature (180-200 о С) [2,[36][37][38][39][40].…”