手性硅烷对环状脂肪族 N-酰亚胺鎓离子的催化不对称加成反应。
Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N-Acyliminium Ions.
机构信息
Homogeneous Catalysis, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der, Ruhr, Germany.
Department of Emerging Materials Science, Daegu Gyeongbuk Institute of Science and Technology (DGIST), 333, Techno Jungang-daero, Hyeonpung-myeon, Dalseong-gun, Daegu (Republik of, Korea.
出版信息
Angew Chem Int Ed Engl. 2022 Feb 21;61(9):e202115036. doi: 10.1002/anie.202115036. Epub 2022 Jan 12.
Strong and confined imidodiphosphorimidate (IDPi) catalysts enable highly enantioselective substitutions of cyclic, aliphatic hemiaminal ethers with enol silanes. 2-Substituted pyrrolidines, piperidines, and azepanes are obtained with high enantioselectivities, and the method displays a broad tolerance of various enol silane nucleophiles. Several natural products can be accessed using this methodology. Mechanistic studies support the intermediacy of non-stabilized, cyclic N-(exo-acyl)iminium ions, paired with the confined chiral counteranion. Computational studies suggest transition states that explain the observed enantioselectivity.
强而受限的亚氨基二膦亚氨基咪唑（IDPi）催化剂可实现环状脂肪族半缩醛醚与烯醇硅烷的高对映选择性取代。高对映选择性地获得 2-取代吡咯烷、哌啶和氮杂环庚烷，该方法对各种烯醇硅烷亲核试剂具有广泛的耐受性。可以使用这种方法获得几种天然产物。机理研究支持非稳定的、环状 N-(外酰基)亚胺鎓离子中间体的存在，与受限的手性抗衡阴离子配对。计算研究表明过渡态可以解释观察到的对映选择性。
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