111035-95-1Relevant articles and documents
Bifunctional Metal-Organic Layers for Tandem Catalytic Transformations Using Molecular Oxygen and Carbon Dioxide
Jiang, Xiaomin,Lan, Guangxu,Lin, Wenbin,Ni, Kaiyuan,Quan, Yangjian,Shi, Wenjie,Song, Yang,Wang, Cheng
supporting information, p. 16718 - 16724 (2021/10/21)
Tandem catalytic reactions improve atom- and step-economy over traditional synthesis but are limited by the incompatibility of the required catalysts. Herein, we report the design of bifunctional metal-organic layers (MOLs), HfOTf-Fe and HfOTf-Mn, consisting of triflate (OTf)-capped Hf6 secondary building units (SBUs) as strong Lewis acidic centers and metalated TPY ligands as metal active sites for tandem catalytic transformations using O2 and CO2 as coreactants. HfOTf-Fe effectively transforms hydrocarbons into cyanohydrins via tandem oxidation with O2 and silylcyanation whereas HfOTf-Mn converts styrenes into styrene carbonates via tandem epoxidation and CO2 insertion. Density functional theory calculations revealed the involvement of a high-spin FeIV (S = 2) center in the challenging oxidation of the sp3 C-H bond. This work highlights the potential of MOLs as a tunable platform to incorporate multiple catalysts for tandem transformations.
Kinetics of Sodium Borohydride Reduction of α-Substituted Benzyl Phenyl Ketones and Equilibria in Their Cyanohydrin Formation
Krishnan, Kp.,Chandrasekaran, J.
, p. 595 - 597 (2007/10/02)
The rate constants for the sodium borohydride reduction of benzyl phenyl ketone and its α-methoxy, α-acetoxy and α-hydroxy derivatives have been measured in propan-2-ol.The rate data indicate that the introduction of a polar substituent in α-position increases the reaction rate, the order in α-substituents being OMe > OH > OAc > H. α-Acetoxybenzyl phenyl ketone reacts slower than expected because of electronic effects.The observed behaviour is explained on the basis of a conformational effect.The equilibrium constants for the formation of cyanohydrins from the above ketones have also been determined; these are parallel to the rate constants for borohydride reduction.