九州大学 研究者情報
総説一覧
森本 浩之(もりもと ひろゆき) データ更新日:2019.06.08

講師 /  薬学研究院 創薬科学部門 生命薬学


総説, 論評, 解説, 書評, 報告書等
1. Kazuhiro Morisaki, Hiroyuki Morimoto, Kazushi Mashima, Takashi Ohshima, Development of direct enantioselective alkynylation of αketoester and α-ketiminoesters catalyzed by phenylbis(oxazoline)Rh(III) complexes, Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, 10.5059/yukigoseikyokaishi.76.226, 2018.01, [URL], Direct catalytic enantioselective alkynylation of carbonyl compounds and imines is one of the most efficient approaches for the synthesis of propargylic alcohols and propargylamines, which are potent building blocks for synthesizing functionalized molecules. While a variety of methods for the reactions with aldehydes and aldimines have been established, the reactions with ketones and ketimines remain underdeveloped due to their reduced reactivity and difficulty in stereocontrol. In this account, we summarized our studies on direct enantioselective alkynylation reaction of α-ketoester and α-ketiminoesters catalyzed by phenylbis(oxazolinephebox)-rhodium(III) complexes, affording enantioenriched propargyl alcohols and propargylamines with a tetrasubsti-tuted carbon stereocenter under proton-transfer conditions. The catalytic system was compatible to a wide range of functional groups, including electrophilic formyl groups, and allowed for the development of an efficient method to access enantioenriched α-CF3-substituted thalidomide analogs. Mechanistic studies revealed that generation of the (alkynyl(phebox)Rh(III) complex from the (diacetatophebox)Rh(III) complex determined the overall reaction rate in the initial stages of the reaction. These results, along with the observed facile exchange of the alkynyl ligand on the (alkynylphebox)Rh(III) complexes, led us to use (trimethylsilylethynylphebox)Rh(III) complexes as a new pre-catalyst. The new catalytic system with (trimethylsilylethynylphebox)Rh (III) precatalysts exhibited enhanced catalytic performance, reduced catalyst loading to as low as 0.5 mol%, and expanded the substrate scope of the reaction with less reactive α-ketiminophos-phonate and cyclic N-sulfonyl α-ketiminoesters..
2. 森崎 一宏, 森本 浩之, 大嶋 孝志, 真島 和志, Direct Enantioselective Alkynylation of α-Ketoesters and α-Ketiminoesters Catalyzed by [Bis(oxazoline)phenyl]rhodium(III) Complexes, Heterocycles, 2017.01.
3. Kazuhiro Morisaki, Hiroyuki Morimoto, Kazushi Mashima, Takashi Ohshima, Direct enantioselective alkynylation of α-ketoesters and α-ketiminoesters catalyzed by [bis(oxazoline)phenyl]rhodium(III) complexes, Heterocycles, 10.3987/REV-16-SR(S)4, 2017, [URL], This review summarizes our studies of the direct enantioselective alkynylation of α-ketoesters and α-ketiminoesters catalyzed by [bis(oxazoline)phenyl]rhodium(III) ((phebox)Rh(III)) complexes. The reactions provide chiral α-tetrasubstituted propargyl alcohols and propargylamines under proton-transfer conditions in high yield and with high enantioselectivity. The unique nature of (phebox)Rh(III) complexes allows the reactions to occur in the presence of various functional groups, including an electrophilic aldehyde functionality. Mechanistic studies revealed that the generation of (alkynyl)Rh(III) complexes limited the overall reactivity, which led us to use (trimethylsilylethynyl)(phebox)Rh(III) complexes as efficient pre-catalysts. The use of (trimethylsilylethynyl)(phebox)Rh(III) complexes reduced catalyst loading to as low as 0.5 mol%, and expanded the substrate scope to unprecedented α-ketiminophosphonate and cyclic N-sulfonyl α-ketiminoesters..
4. 森本 浩之, 単純アルケンに対する酸素求核剤の直接的触媒的anti-Markovnikov付加反応, 有機合成化学協会誌, 2014.12,  単純アルケンへの酸素求核剤の付加反応は、通常Markovnikov則に従ってカルボカチオンがより安定な側に選択的に進行する。そのため、一般にanti-Markovnikov型の生成物を得るためには、ヒドロホウ素化とそれに続く酸化などの段階的な手法をとる必要があった。本総説では、金属触媒および光触媒を活用し、単純アルケンから直接的に種々の酸素求核剤のanti-Markovnikov付加体を高選択的に得た最近の例を紹介する。.
5. Hiroyuki Morimoto, Direct catalytic anti-Markovnikov addition reactions of oxygen nucleophiles to simple Alkenes, Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, 10.5059/yukigoseikyokaishi.72.1402, 2014.12, [URL], Development of direct catalytic anti-Markovnikov addition reactions of oxygen nucleophiles to simple alkenes is a difficult challenge due to the propensity to form Markovnikov adducts under ordinary reaction conditions. Herein selected recent examples that realize these reactions with high anti-Markovnikov selectivity are summarized..
6. 清水悠平, 森本 浩之, 大嶋 孝志, 安定なアミド結合を温和に切断!-強酸、強塩基を必要としないアミド切断反応の開発, 化学 2012 Vol. 67 (12) pp.70-71, 2012.12.
7. 森本 浩之, 四置換炭素構築を可能とするイミンの直接的触媒的不斉アルキニル化, ファルマシア, 2012, 48, 329., 2012.05.

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