599-75-7Relevant articles and documents
Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0)
Entz, Emily D.,Hooker, Leidy V.,Neufeldt, Sharon R.,Russell, John E. A.
supporting information, p. 15454 - 15463 (2020/10/18)
Current methods for Suzuki-Miyaura couplings of nontriflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe3, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the presence of aryl chlorides. This selectivity was exploited in the first Ni-catalyzed C-O-selective Suzuki-Miyaura coupling of chlorinated phenol derivatives where the oxygen-containing leaving group is not a fluorinated sulfonate such as triflate. Computational studies suggest that the origin of divergent selectivity between PMe3 and other phosphines differs from prior examples of ligand-controlled chemodivergent cross-couplings. PMe3 effects selective reaction at tosylate due to both electronic and steric factors. A close interaction between nickel and a sulfonyl oxygen of tosylate during oxidative addition is critical to the observed selectivity.
Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
, p. 5025 - 5038 (2017/10/06)
Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
Iodine-induced synthesis of sulfonate esters from sodium sulfinates and phenols under mild conditions
Gao, Jian,Pan, Xiaojun,Liu, Juan,Lai, Junyi,Chang, Liming,Yuan, Gaoqing
, p. 27439 - 27442 (2015/03/31)
An iodine-induced synthesis of sulfonate esters via cross-coupling reactions of sodium sulfinates with phenols is reported. This synthetic route is low-cost, facile, green and efficient, and could afford the target products with good to excellent yields u
