American Chemical Society
jo7b01204_si_001.pdf (25.38 MB)

Palladium-Catalyzed SN2′-Cyclization of Ambivalent (Bromoalkadienyl)malonates: Preparation of Medium- to Large-Membered Endocyclic Allenes

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journal contribution
posted on 2017-06-22, 00:00 authored by Hiroaki Ichio, Hidetoshi Murakami, Yen-Chou Chen, Tamotsu Takahashi, Masamichi Ogasawara
A palladium-catalyzed reaction for preparing various endocyclic allenes was developed. The substrates for the reaction were readily available ω-(pronucleophile-tethered)-3-bromo-1,3-alkadienes, and a palladium-catalyst facilitated their unimolecular SN2′-cyclization in the presence of potassium tert-butoxide to give the corresponding 9- to 16-membered endocyclic allenes in fair yields of up to 67% together with the dimeric 16- to 32-membered endocyclic bis-allenes and other oligomeric/polymeric intermolecular reaction products. For higher yields of the monomeric endocyclic allenes, the reaction needed to be conducted under high-dilution conditions. Using a chiral palladium catalyst, axially chiral endocyclic allenes were obtained in up to 70% ee.