ja8b08534_si_007.cif (5.77 MB)

Preferential Photoreaction in a Porous Crystal, Metal–Macrocycle Framework: PdII-Mediated Olefin Migration over [2+2] Cycloaddition

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posted on 08.11.2018, 00:00 by Hirotaka Yonezawa, Shohei Tashiro, Takafumi Shiraogawa, Masahiro Ehara, Rintaro Shimada, Takeaki Ozawa, Mitsuhiko Shionoya
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.