N-フルオレニルイミンを一電子還元剤かつアミノアルキル化剤として，ニトロアルカンの脱ニトロアミノアルキル化反応を達成した．本手法は，ニトロアルカンの還元的ホモログ化反応とみなすことができ，天然物などに見られるβ位に四級炭素を有するアミンを効率よく合成できるため有用である．We have achieved the denitrative aminoalkylation reaction of nitroalkanes using N-fluorenylimine as a sin-gle-electron reducing agent and aminoalkylating agent. This reaction can be considered as a reductive ho-mologation reaction of nitroalkanes, enabling efficient synthesis of amines with a quaternary carbon at the β-position, which are often found in natural products.中尾 佳亮ニトロ基を脱離基とする置換反応の創出19Yoshiaki NAKAO佐藤 隆章20Takaaki SATO（2022採択）Development of Substitution Reactions of Nitro Compounds(Project 2022)プロリン・N-メチルアミノ酸選択的なペプチド直接修飾法の開発（2022採択）Development of Proline- and N-Methyl Amino Acid-selective Functionalization of Peptides(Project 2022)33ring-opening of cyclopropanol derivatives being considered as the most promising strategy. We have suc-ceeded in developing the novel preparation method of potassium homoenolate equivalents directlyl from readily available allylic alcohols in the presence of a potassium carboanion. These species are highly reactive and possess two nucleophilic sites, thus offering an easy access to β-functionalized and α,β-difunctional-ized carbonyl compounds and their derivatives.本研究では，生物活性ペプチドに含まれるアミド基のうち，プロリンアミドとN-メチルアミドが三級アミドである点に着目し，これらのアミド基選択的に作用する求核付加反応の開発に取り組んだ．トリペプチドに対し，イリジウム触媒と(Me2SiH)2Oを加えた後，酸と求核剤を添加すると，プロリンアミドまたはN-メチルアミド選択的にMannich反応が進行した．また，本反応では，様々なアミノ酸側鎖が共存できることが分かった．今後は，確立した反応条件を生物活性ペプチドの直接的な化学修飾へと応用し，より高機能なペプチド医薬品の開発へと展開していく．We developed proline and N-methyl amide-selective nucleophilic addition to biologically active peptides. Iridium-catalyzed hydrosilylation of tripeptides, followed by acid-mediated Mannich reaction enabled direct functionalization of tertiary amides in the presence of various amino acid side chains. The developed method will be applicable to biologically active peptides including proline and N-methyl amides, affording products with better function.
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