2024-03-29T07:09:39Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/717362022-11-17T02:08:08Zhdl_2115_20045hdl_2115_139Double Asymmetric Hydrogenation of Linear β,β-Disubstituted α,β-Unsaturated Ketones into γ-Substituted Secondary Alcohols using a Dual Catalytic System1000080282721Arai, NoriyoshiSatoh, HironoriKomatsu, Ryo1000050201968Ohkuma, Takeshiopen accessThis is the peer-reviewed version of the following article: Chemistry-A European journal 23 (37) 8806-8809 2017-07-03, which has been published in final form at https://doi.org/10.1002/chem.201701527. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-Archiving.570Double asymmetric hydrogenation of linear β,β‐disubstituted α,β‐unsaturated ketones catalyzed by the DM‐SEGPHOS/DMAPEN/RuII complex with t‐C4H9OK afforded the γ‐substituted secondary alcohols in high diastereo‐ and enantioselectivities. Some mechanistic experiments suggested that two different reactive species, type (I) and (II), were reversibly formed in this catalytic system: Type (I) with the diamine ligand DMAPEN enantioselectively hydrogenated the enones into the chiral allylic alcohols, and type (II) without the diamine ligand diastereoselectively hydrogenated the allylic alcohols into the γ‐substituted secondary alcohols. This dual catalysis protocol was successfully applied to the reaction of a variety of aliphatic‐ and aromatic‐substituted enone substrates.Wiley2017-07-03engjournal articleAMhttp://hdl.handle.net/2115/71736https://doi.org/10.1002/chem.201701527284073160947-6539Chemistry - A European Journal233788068809https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/71736/1/HUSCAP-Manuscript-Double%20HG.pdfapplication/pdf248.31 KB2017-07-03