112459-98-0Relevant academic research and scientific papers
An efficient iron catalyzed regioselective acylative cleavage of ethers: Scope and mechanism
Bodduri, V.D. Vijaykumar,Choi, Kyung-Min,Vaidya, Raghavender Rao,Patil, Kalpesh,Chirumarry, Sridhar,Jang, Kiwan,Yoon, Yong-Jin,Falck, John R.,Shin, Dong-Soo
supporting information, p. 7089 - 7093 (2015/12/01)
A method involving iron catalyzed acylative cleavage of cyclic and acyclic ethers with acyl/aroyl chlorides has been studied to produce chloroesters and esters respectively. Examination of the scope revealed that less electron rich alkyl group in unsymmetric, acyclic ether was acylated while the chloride derived from the counterpart moiety was volatile and difficult to isolate. In contrast, α-branched cyclic ethers were converted to the corresponding primary ester and secondary chloride. Steric hindrance of ether also plays an important role in acylative C-O bond cleavage. The mechanism of ether cleavage is proposed to involve a single electron initiated SN1 dissociative pathway.
Lewis Acid Catalysis of Photochemical Reactions. 7. Photodimerization and Cross-Cycloaddition of Cinnamic Esters
Lewis, Frederick D.,Quillen, Suzanne L.,Hale, Paul D.,Oxman, Joe D
, p. 1261 - 1267 (2007/10/02)
The effects of Lewis acid complexation upon the molecular structure, solid-state photodimerization, and solution dimerization and cross-cycloaddition of cinnamic esters have been investigated.Comparison of crystal structures for free and SnCl4-complexed ethyl cinnamate indicates that the enone double bonds are lengthened, the single bonds are shortened, and the enone conformation changes from s-cis to s-trans upon complexation.These changes are consistent with calculated changes in ? bonding and net charges.Solid-state photodimerization of free and complexed cinnamic esters and related molecules yield syn head-to-tail (α-truxillate) dimers.In most cases the Lewis acid complexes dimerize more efficiently and stereoselectively than the free esters.Photodimerization and cross-cycloaddition of methyl cinnamate in dilute solution is also catalyzed by Lewis acids.The mechanism of these reactions involves electronic excitation of a ground-state methyl cinnamate-Lewis acid complex followed by reaction of the excited complex with ground-state ester (dimerization) or simple olefin (cross-cycloaddition).The catalytic effect of Lewis acids is attributed to an increase in excited-state lifetime and reactivity.
