86724-26-7Relevant academic research and scientific papers
Merging Halogen-Atom Transfer (XAT) and Copper Catalysis for the Modular Suzuki-Miyaura-Type Cross-Coupling of Alkyl Iodides and Organoborons
Zhang, Zhenhua,Górski, Bartosz,Leonori, Daniele
supporting information, p. 1986 - 1992 (2022/02/01)
We report here a mechanistically distinct approach to achieve Suzuki-Miyaura-type cross-couplings between alkyl iodides and aryl organoborons. This process requires a copper catalyst but, in contrast with previous approaches based on palladium and nickel
The photochemistry of the 4-cyanobenzoic acid esters of trans- and cis-2-phenylcyclohexanol
Pincock,Rifai,Stefanova
, p. 63 - 69 (2007/10/03)
Irradiation of trans-2-phenylcyclohexyl 4-cyanobenzoate (4) in methanol results in formation of the 1-phenylcyclohexene and 4-cyanobenzoic acid as the major products. The mechanism proposed for this example of the Norrish Type II-like reaction, normally inefficient for the π,π*state of esters, begins with intramolecular electron transfer in the excited singlet state. The next step, intramolecular proton transfer, is highly exergonic as a result of the increased acidity of the benzylic hydrogen of the radical cation and the increased basicity of the carbonyl oxygen of the radical anion. The final step is cleavage of the 1,4-biradical. This mechanism is proposed on the basis of product studies, absorption spectra, fluorescence spectra, oxidation and reduction potentials, and nanosecond laser flash photolysis spectra. The stereochemical requirements for the process have also been examined using solution NMR, the X-ray structure, and MM3 calculations. The stereoisomer, cis-2-phenylcyclohexyl 4-cyanobenzoate (5), undergoes cis to trans isomerization before photofragmentation. Photolysis of the cis isomer in methanol-OD demonstrated that the cis to trans isomerization occurred by inversion at C1.
Stereo and regioselectivity in the phenylation of cationic allylpalladium(II) α-diimine complexes by tetraphenylborate anion
Crociani, Bruno,Antonaroli, Simonetta,Bianca, Francesca Di,Fontana, Alberta
, p. 21 - 26 (2007/10/02)
The reaction of the cationic complex 3-cyclohexenyl>(py-2-CH=NC6H4OMe-4)>+ (1) with BPh4- in the presence of fumaronitrile yields trans-3-methoxy-6-phenylcyclohexene (2a) and trans-4-methoxy-3-phenyl-cycohexene (2b), in ca. 1:1 molar ratio.The trans stereochemistry of these products implies that the phenylation of the allyl ligand involves prior transfer of a phenyl group from BPh4- to the metal, followed by reductive coupling of the organic moieties.In the reaction of 3-1,1-R1,R2-C3H3)(N-N')>+ (3) 1 = H, R2 = Ph, Me; R1 = R2 = Me> with BPh4- in the presence of activated olefins, both regioisomers PhCH2-CH=CR1R2 (4a) and CH2=CH-CR1R2Ph (4b) are formed with a relative ratio which depends essentially on the allylic substituents: R1 = H, R2 = Ph, 4a above 98percent; R1 = H, R2 = Me, 4a 75-67percent; R1 = R2 = Me, 4a 64-58percent.The regioisomer distribution is very little affected by the nature of the α-diimine, of the activated olefin, and of the solvent.For R1 = H and R2 = Ph, Me, the olefinic product 4a has a trans (E) geometry.These results have been interpreted in terms of reductive elimination occurring in the intermediate 3-1,1,R1,R2C3H3)(N-N')> with a ?-N monodentate α-diimine ligand.
OXIDATION OF N-ALKYL-N'-TOSYLHYDRAZINES WITH Hg(OAc)2. A NEW SYNTHESIS OF ETHERS
Gasparrini, F.,Caglioti, L.,Misiti, D.,Palmieri, G.,Ballini,R.
, p. 3609 - 3613 (2007/10/02)
N-Alkyl-N'-tosylhydrazines with Hg(OAc)2 in the presence of alcohols or phenol give high yields of corresponding ethers.Reactions in the presence of acetic acid are also examined.
