51857-41-1Relevant articles and documents
Catalytic Activation of Unstrained C(Aryl)-C(Alkyl) Bonds in 2,2′-Methylenediphenols
Dong, Guangbin,Ratchford, Benjamin L.,Xue, Yibin,Zhang, Rui,Zhu, Jun
, p. 3242 - 3249 (2022/02/23)
Catalytic activation of unstrained and nonpolar C-C bonds remains a largely unmet challenge. Here, we describe our detailed efforts in developing a rhodium-catalyzed hydrogenolysis of unstrained C(aryl)-C(alkyl) bonds in 2,2′-methylenediphenols aided by removable directing groups. Good yields of the monophenol products are obtained with tolerating a wide range of functional groups. In addition, the reaction is scalable, and the catalyst loading can be reduced to as low as 0.5 mol %. Moreover, this method proves to be effective to cleave C(aryl)-C(alkyl) linkages in both models of phenolic resins and commercial novolacs resins. Finally, detailed experimental and computational mechanistic studies show that with C-H activation being a competitive but reversible off-cycle reaction, this transformation goes through a directed C(aryl)-C(alkyl) oxidative addition pathway.
CHIRAL PHOSPHORUS COMPOUNDS
-
Page/Page column 31, (2008/12/04)
The present invention provides P-chiral compounds of general formula (II) and (III): wherein at least one of R21, R25, R26 and R30 is independently selected from C1-4 alkyl, CF3, C1-4 alkoxy, phenyl and benzyloxy and the remaining substituents selected from R21, R25, R26 and R30 are hydrogen; at least one of R22, R24, R27 and R29 are independently selected from C1-4 alkyl, CF3, C1-4 alkoxy, phenyl and benzyloxy and the remaining substituents selected from R22, R24, R27 and R29 are hydrogen; and R23 and R28 are independently selected from hydrogen, C1-4 alkyl, CF3, C1-4 alkoxy, phenyl and benzyloxy; Formula (III): wherein at least one of R21, R25, R26 and R30 is independently selected from phenyl and benzyloxy and the remaining substituents selected from R21, R25, R26 and R30 are hydrogen; and R22, R23, R24, R27, R28 and R29 are independently selected from hydrogen, C1-4 alkyl, CF3, C1-4 alkoxy, phenyl and benzyloxy.wherein at least one of R21, R25, R26 and R30 is independently selected from phenyl and benzyloxy and the remaining substituents selected from R21, R25, R26 and R30 are hydrogen; and R22, R23, R24, R27, R28 and R29 are independently selected from hydrogen, C1-4 alkyl, CF3, C1-4 alkoxy, phenyl and benzyloxy.
Novel Antioxidants: Unexpected Rearrangements in the Radical Cyclization Approach to 2,3-Dihydrobenzo[b]thiophene-5-ol Derivatives
Malmstroem, Jonas,Gupta, Vijay,Engman, Lars
, p. 3318 - 3323 (2007/10/03)
The novel α-tocopherol analogue 3,3,4,6,7-pentamethyl-2,3-dihydrobenzo[b]thiophene-5-ol (4a) was prepared by cyclodehydration of the aryl 2-hydroxyalkyl sulfide 6 in concentrated sulfuric acid. Aromatic bromination and dehydration of alcohol 6 furnished the 2-bromoaryl methallyl sulfide 10a as the kinetic product and the 2-bromoaryl 2-methyl-2-propenyl sulfide 11a as the thermodynamic one. Radical cyclization of these compounds afforded the desired 2,3-dihydrobenzo[b]-thiophene derivative 12 in addition to a rearranged isomer 13 thereof. It is proposed that the transformation of compound 10a to 13 occurs via 6-endo cyclization, β-scission, and subsequent 5-exo cyclization. The radical cyclization of the 2-bromoaryl allyl sulfide 16, unsubstituted in the allylic moiety, furnished only 2,3-dihydrobenzo[b]thiophene-5-ol derivative 17.