65627-27-2Relevant academic research and scientific papers
Preferential Photoreaction in a Porous Crystal, Metal-Macrocycle Framework: PdII-Mediated Olefin Migration over [2+2] Cycloaddition
Yonezawa, Hirotaka,Tashiro, Shohei,Shiraogawa, Takafumi,Ehara, Masahiro,Shimada, Rintaro,Ozawa, Takeaki,Shionoya, Mitsuhiko
, p. 16610 - 16614 (2018)
A nanosized confined space with well-defined functional surfaces has great potential to control the efficiency and selectivity of catalytic reactions. Herein we report that a 1,6-diene, which normally forms an intramolecular [2+2] cycloadduct under photoirradiation, preferentially undergoes a photoinduced olefin migration in a porous crystal, metal-macrocycle framework (MMF), and alternatively [2+2] cycloaddition is completely inhibited in the confined space. A plausible reaction mechanism for olefin migration triggered by the photoinduced dissociation of the Pd-Cl bond is suggested based on UV-vis diffuse reflectance spectroscopy, single-crystal XRD, and MS-CASPT2 calculation. The substrate scope of the photoinduced olefin migration in MMF was also examined using substituted allylbenzene derivatives.
Concerning the Mechanism of the Reaction of LiAlH4 with Alkyl Halides
Ashby, E. C.,Pham, T. N.,Amrollah-Madjdabadi, A.
, p. 1596 - 1603 (2007/10/02)
A detailed study of the mechanism of reaction of LiAlH4 with alkyl halides has been carried out with special emphasis on the use of radical probes.The data presented strongly support the validity of using radical probes in this reaction as an indication of an electron-transfer process.These studies also suggest a radical chain process (hydrogen atom transfer) in addition to the halogen atom transfer process on which we reported earlier.Studies to determine the influence of impurities as well as a potential metal-halogen exchange process are also reported.
