2024-03-29T09:44:37Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/805682022-11-17T02:08:08Zhdl_2115_52005hdl_2115_52004Copper(I)-Catalyzed Boryl Substitution of 1-Trifluoromethyl Allenes for the Synthesis of 3-Boryl-Substituted 1,1-gem-DifluorodienesAkiyama, SotaNomura, SyogoKubota, Koji1000090282300Ito, Hajimeopen accessThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of organic chemistry, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.joc.9b03353.437A method to synthesize 3-boryl-1,1-gem-difluorodienes via the copper(I)-catalyzed boryl substitution of trifluoromethyl-substituted allenes was developed. The borylated compounds were obtained up to 91% yield with excellent selectivity. We proposed that the reaction proceeded via gamma-selective borylcupration into the trifluoromethyl-substituted alien; followed by copper(I)-beta-fluoro elimination. Subsequent transformations of the borylation product by Suzuki-Miyaura cross-coupling or Diels-Alder reaction provided various compounds bearing a difluoro moiety, which are difficult to synthesize by existing methods.American Chemical Society2020-02-04engjournal articleAMhttp://hdl.handle.net/2115/80568https://doi.org/10.1021/acs.joc.9b033530022-3263Journal of organic chemistry85641724181https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/80568/1/Akiyama%20Sota_HUSCAP.pdfapplication/pdf873.94 KB2020-02-04