15948-70-6Relevant 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
supporting information, p. 16610 - 16614 (2018/12/11)
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.
Efficient allyl to propenyl isomerization in functionally diverse compounds with a thermally modified Grubbs second-generation catalyst
Hanessian, Stephen,Giroux, Simon,Larsson, Andreas
, p. 5481 - 5484 (2007/10/03)
Heating compounds containing C-allylic appendages in MeOH in the presence of 10 mol % of Grubbs second-generation catalyst at 0.075 M substrate concentration leads to the corresponding 2-propenyl derivatives without further conjugation in the cases of ketones, esters, and lactams. The reaction is applicable to a large variety of functionally relevant terminal olefins, including O- and N-allyl ethers.
