Ni(0)-Catalyzed Rearrangement of Vinylcyclobutanones (VCBOs) to Synthesize Six-Membered Non-Conjugated Enones
Jiguo Ma1, Jicheng Duan1, Zhi-Xiang Yu1
1Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Abstract:
We report here the first nickel-catalyzed rearrangement of vinylcyclobutanones (VCBOs) under mild conditions to synthesize non-conjugated cyclohexenone derivatives, which so far do not have many ways to be accessed. The reaction exhibits a wide substrate scope with reaction yields up to 98 %. This VCBO rearrangement can also be used to access various n/6 (n=5-8) bicyclic products efficiently. Furthermore, mechanism of this rearrangement has been investigated using DFT calculations, showing that vinyl group-assisted cyclobutanone C-C cleavage is easy with a computed activation free energy of 18.1 kcal/mol.
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