2024-03-29T15:01:57Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/791092022-11-17T02:08:08Zhdl_2115_20045hdl_2115_139Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related DerivativesAkiyama, SotaKubota, KojiMikus, Malte S.Paioti, Paulo H. S.Romiti, FilippoLiu, QingheZhou, YuebiaoHoveyda, Amir H.Ito, Hajimeboroncopperenantioselective catalysisfluorinesynthetic methods437The first catalytic method for diastereo- and enantioselective synthesis of allylic boronates bearing a Z-trisubstituted alkenyl fluoride is disclosed. Boryl substitution is performed with either a Z- or E-allyldifluoride and is catalyzed by bisphosphine/Cu complexes, affording products in up to 99 % yield with >98:2 Z/E selectivity and 99:1 enantiomeric ratio. A variety of subsequent modifications are feasible, and notable examples are diastereoselective additions to aldehydes/aldimines to access homoallylic alcohols/amines containing a fluorosubstituted stereogenic quaternary center.Wiley-BlackwellJournal Articleapplication/pdfhttp://hdl.handle.net/2115/79109https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/79109/1/manuscript.pdf1433-7851Angewandte chemie-international edition583511998120032020-06-13enginfo:doi/10.1002/anie.201906283This is the peer reviewed version of the following article: S. Akiyama, K. Kubota, M. S. Mikus, P. H. S. Paioti, F. Romiti, Q. Liu, Y. Zhou, A. H. Hoveyda, H. Ito, Angew. Chem. Int. Ed. 2019, 58, 11998, which has been published in final form at https://doi.org/10.1002/anie.201906283. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.author