富山大学工学部 応用化学コース 有機合成化学研究室 Synthetic Organic Chemistry

Make an impac. Make a difference.

有機合成化学研究室

Make an impac. Make a difference.

研究紹介

アルキニルスズを用いる新規分子変換反応

ラジカル反応によるジアステレオ選択的なホモアリルアルコールの合成

The trialkylborane/O2-mediated reaction of propargyl acetates having a tributylstannyl group at an alkyne terminus with aldehydes in a THF–H2O solvent system gave anti-δ,δ-disubstituted homoallylic alcohols with good to high diastereoselectivity. Intriguingly, two alkyl groups derived from trialkylborane were embedded into the reaction product. The trialkylborane plays a key role not only as a radical initiator but also as a source of alkyl radicals.

パラジウム触媒を用いた三成分連結反応

パラジウム触媒を用いた三成分連結反応よるアステレオ選択的なホモアリルアルコールの合成

Controllable Stereoselective Synthesis of (Z) and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction

Diastereoselective synthesis of (Z)- and (E)-homoallylic alcohols using a Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl benzoates, aldehydes, and aryl stannanes was developed, which provides an alternative method for the allylboration of aldehydes using α,γ-diaryl-substituted allylboronates. Both sets of reaction conditions enable access to either (Z)- or (E)-homoallylic alcohols with good to high alkene stereocontrol. The present method showed good functional group compatibility and generality. Efficient chirality transfer reactions to afford enantioenriched (Z)- and (E)-homoallylic alcohols were also achieved.

Palladium-Catalyzed Three-Component Reaction of 3-(Tri-n-butylstannyl)allyl Acetates, Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ-Substituted Allylic Tin Reagents

A three-component reaction of 3-(tri-n–butylstannyl)allyl acetates, aldehydes, and triorganoboranes in the presence of a palladium-Xantphos catalyst system predominately gave (E)-anti-homoallylic alcohols with high diastereoselectivity and good to high levels of alkene stereocontrol. An efficient chirality transfer was observed when an enantioenriched substrate was employed. The reaction was initiated by the formation of an allylic gem-palladium/stannyl intermediate, which subsequently underwent allylation of the aldehyde by an allyltributyltin followed by a coupling reaction of the in-situ-generated (E)-vinylpalladium acetate with the triorganoborane.

Pd-Catalyzed Three-Component Reaction of 3-(Pinacolatoboryl)ally Acetates, Aldehydes, and Organoboranes: A New Entry to Stereoselective Synthesis of (Z)-anti-Homoallylic Alcohols

The Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl acetates, aldehydes, and organoboranes is described. The reaction is initiated by the formation of an allylic gem-palladium/boryl intermediate, which then undergoes allylation of aldehydes by allylboronates followed by a coupling reaction of in situ generated (Z)-vinylpalladium acetates with organoboranes to provide the (Z)-anti-homoallylic alcohols with high levels of diastereoselectivity and alkene stereocontrol.

メンバー紹介

堀野 良和

堀野 良和准教授

HORINO Yoshikazu

略歴

  • 2002年        長崎大学大学院生産科学研究科海洋資源学専攻 博士課程修了 博士(工学)
  • 2000-2002 日本学術振興会特別研究員(DC2)
  • 2002-2003 モンタナ州立大学 博士研究員 Tom Livinghouse研究室
  • 2003-2004 公益財団法人 相模中央化学研究所 触媒化学グループ研究員
  • 2004-2006 日本学術振興会海外特別研究員
  • 2004-2005 ケルン大学 博士研究員 Hans-Günther Schmalz研究室
  • 2005-2006 カリフォルニア大学 バークレー校博士研究員 F. Dean Toste研究室
  • 2006-2007 富山大学 工学部物質生命システム工学科 助手 
  • 2007-2012 富山大学 大学院理工学研究部(工学)助教
  • 2012-           富山大学 大学院理工学研究部(工学)准教授

専門分野

  • 有機合成化学
  • 有機反応化学

研究業績

研究業績

論文・発表

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