Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

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

Palladium-Catalyzed SN2′-Cyclization of Ambivalent (Bromoalkadienyl)malonates: Preparation of Medium- to Large-Membered Endocyclic Allenes
Masamichi Ogasawara, Tamotsu Takahashi, Yen-Chou Chen, Hiroaki Ichio, Hidetoshi Murakami
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.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b01204

DOI: 10.1021/acs.joc.7b01204

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