北川　理
応用化学科 (工学部)
教授
有機合成化学研究室
■専門分野
有機合成化学、構造有機化学
■研究の内容
■研究室分野キーワード
■関連業種
医薬品・農薬・材料関係の分野で、光学活性有機化合物の需要はますます高まっています。光学活性化合物を得るための手法は、産業界ではキラルテクノロジーと呼ばれています。キラルテクノロジーでは、不斉反応や光学分割で使用される不斉分子が成否の鍵を握っています。本研究室では、キラルテクノロジーで利用可能な新たな不斉分子の開発、ならびにこの分子を利用した生理活性化合物の合成について検討しています。
材料・化学
化学工業
■教員研究テーマ
有機合成の新手法の開発ならびに炭素-窒素結合の回転障害により生じる立体異性体に関する研究
■研究室テーマ
①炭素-窒素不斉軸を有するアトロプ異性アニリド誘導体の触媒的不斉合成と応用に関する研究②常温でも分離可能なアミド配座異性体に関する研究③エナンチオマーの不均化現象を利用した新規光学分割法の開発
■相談可能な分野
■保有機器
■研究室のスタンス
キラルな化成品や医薬品の合成
キラルカラム
高性能液体クロマトグラフ
［以上、光学異性体過剰率の決定に利用］
■主な論文
  • Synthesis of optically active N-C axially chiral tetrahydroquinoline and its response to acid-accelerated molecular rotor（2015/07 Chem. Commun.）
  • A comprehensive examination of the selfdisproportionation of enantiomers (SDE) of chiralamides via achiral, laboratory-routine, gravitydriven column chromatography（2015/01 RSC Advances）
  • Relationship between rotational barriers and structures in N-C axially chiral 3,4-dihydroquinolin-2-one and 3,4-dihydrobenzoquinolin-2-one（2015/01 Tetrahedron Letters）
  • Asymmetric Synthesis of Atropisomeric Compounds with an N-C Chiral Axis（2014/01 Org. Prep. Proc. Int.）
  • Chiral initiator-induces self-disproportionation of enantiomers via achiral chromatography: application to enantiomer separation of racemate（2013/09 Tetraheron Letters）
  • Unique Structural Property of 2,4,6-Tri-tert-butylanilides: Isomerization and Switching between Separable Amide Rotamers through the Reaction of Anilide Enolates（2013/05 Chem. Eur. J.）
  • Rotational isomerism in 2,4,6-tri-tert-butylanilides（2013/01 Tetrahedron）
  • Catalytic enantioselective synthesis of atropisomeric 2-aryl-4-quinolinonederivatives with an N-C chiral axis（2012/12 Tetrahedron: Asymmetry）
  • Studies on rotational barriers of N-C axially chiral compounds: increase in the rotational barrier by aromatization（2012/08 Tetrahedron Lett）
  • Self-disproportionation of enantiomers via achiral chromatography: a warning and an extra dimension in optical purifications（2012/06 Chem. Soc. Rev.）
  • Self-Disproportionation Of Enantiomers Of Non-Racemic Chiral Amine Derivatives Through Achiral Chromatography（2012/06 Tetrahedron）
  • 炭素-窒素不斉軸を有する新規アトロプ異性化合物の触媒的不斉合成と不斉反応への応用（2011/09 有機合成化学協会誌）
  • Notable Structural Property of 2,4,6-Tri-tert-butylanilide Enolates: Interconversion between the Rotamers and Their Reactivity（2011/05 Organic Letters）
  • Intramolecular Diels-Alder Reaction of N-Allyl 2-Furoyl Amides: Effect of Steric Strain and Amide Rotational Isomerism（2011/01 Tetrahedron Lett）
  • Catalytic Enantioselective Synthesis of Atropisomeric Indoles with an N-C Chiral Axis.（2010/05 Chem. Eur. J.）
  • Atropisomeric lactam chemistry: catalytic enantioselective synthesis, application to asymmetric enolate chemistry and synthesis of key intermediates for NET inhibitors（2010/01 Tetrahedron）
  • Highly Selective Stereodivergent Synthesis of Separable Amide Rotamers Using Pd Chemistry and Their Thermodynamic Behaviors.（2009/05 Chem. Eur. J.）
  • 触媒的不斉芳香族アミノ化反応を利用する炭素-窒素軸不斉化合物の効率的合成法の開発（2009/03 薬学研究の進歩　研究成果報告集）
  • Stereoselective synthesis of separable amide rotamers usingp-allyl-Pd catalyst and their thermodynamic behavior（2008/08 Tetrahedron Lett.）
  • Catalytic Enantioselective Synthesis of Key Intermediates for NET Inhibitors using Atropisomeric Lactam Chemistry（2008/02 Tetrahedron Lett.）
  • Highly Enantioselective Synthesis of Atropisomeric Anilide Derivatives through Catalytic Asymmetric N-Arylation: Conformational Analysis and Application to Asymmetric Enolate Chemistry.（2006/09 J. Am. Chem. Soc.）
  • ヨードメチルシクロプロパン誘導体を用いるヨウ素原子移動型ラジカル[3+2]付加環化反応（2006/06 FIU Letters）
  • Catalytic Asymmetyric Desymmetrization of meso-Diamide derivatives through Enantioselective N-Allylation Using Chiral -Allyl Pd Catalyst: Improvement and Reversal of the Enantioselectivity.（2006/02 J. Org. Chem.）
  • Efficient Synthesis of Optically Active Atropisomeric Anilides through Catalytic Asymmetric N-Arylation Reaction.（2005/03 J. Am. Chem. Soc.）
  • Catalytic Asymmetric Synthesis of Vicinal Diamine Derivatives through Enantioselective N-Allylation using Chiral -Allyl Pd-Catalyst.（2004/10 Org. Lett.）
  • Iodine Atom Transfer [3+2] Cycloaddition Reaction with Alkenes Using Unsymmetrical Allylated Active Methine Radicals.（2004/03 J. Org. Chem.）
  • 新規ヨード環化反応ならびにラジカル付加環化反応の開発（2004/01 TCIメール）
  • Synthesis of Optically Active Atropisomeric Anilide Derivatives through Diastereoselective N-Allylation with a Chiral Pd- -Allyl Catalyst.（2003/10 J. Org. Chem.）
  • Iodine Atom Transfer [3+2] Cycloaddition Reaction with Electron-rich Alkenes using N-Tosyl Iodoaziridine Derivatives as Novel Azahomoallyl Radical Precursors.（2003/02 J. Org. Chem.）
  • Catalytic Asymmetric Synthesis of Optically Active Atropisomeric Anilides through Enantioselective N-Allylation with Chiral Pd-tol-BINAP Catalyst.（2002/11 J. Org. Chem.）
  • Radical Cascade Reaction with 1,4-Dienes and 1,4-Enynes using 2-(Iodomethyl)cyclopropane-1,1-dicarboxylate as a Homoallyl Radical Precursor: One-step Synthesis of Bicyclo[3.3.0]octane Derivatives.（2002/03 Org. Lett.）
  • Radical [3+2] Cycloaddition Reaction with Various Alkenes Using Iodomethylcyclopropane Derivatives as New Homoallyl Radical Precursors.（2002/01 J. Org. Chem）
  • Iodocarbocyclization and Intramolecular Carbometalation Strategies for Carbocycles.（2002/01 有機合成　創造の軌跡　ー126のマイルストーンー　有機合成化学協会編）
  • Iodoaziridine Derivatives as Novel Azahomoallyl Radical Precursors for [3+2] Cycloaddition Reactions with Alkenes（2001/07 Angew. Chem. Int. Ed.）
  • Synthesis of Optically Active Aldol Derivatives through Chilarity Transfer Type 1,2-Wittig Rearrangement of -Alkoxycarboxamides.（2001/07 Tetrahedron Lett.）
  • 光学活性アトロプ異性アニリド誘導体の合成と不斉反応への応用（2001/07 有機合成化学協会誌）
  • Radical [3+2] Cycloaddition Reaction with Alkenes using Dimethyl 2-Iodomethylcyclopropane-1,1-dicarboxylate as a New Homoallyl Radical Precursor.（2001/03 Tetrahedron Lett.）
  • Stereoselective Synthesis of Diastereomeric Atropisomeric Lactam with Various Ring Sizes and Their Structural Characterization.（2000/11 Tetrahedron Lett.）
  • Intramolecular Carbostannation Reaction of Active Methine Compounds with an Unactivated C-C -Bond Mediated by SnCl4-Et3N.（2000/09 J. Org. Chem.）
  • Synthesis of Optically Active 5-Substituted-2-pyrroridinone Derivatives Having Atropisomeric Structure and 3,5-Cis-selective Reaction of Their Enolates with Electrophiles.（2000/02 J. Org. Chem.）
  • Efficient Synthesis of Various Atropisomeric Amides in Optically Pure Forms and Their Application to Asymmetric Reactions.（1999/10 Tetrahedron Lett.）
  • Iodocarbocyclization and Iodoaminocyclization Reactions mediated by a Metallic Reagent.（1999/08 Synlett）
  • Alkaline Metallic Reagent-catalyzed Hydrocarbocyclization Reaction of Various Active Methine Compounds Having an Unactivated 4-Alkynyl or Allenyl Group.（1999/06 Tetrahedron Lett.）
  • Intramolecular Carbostannation Reaction of Active Methine Compounds Having an Allenyl Group Mediated by SnCl4-Et3N.（1999/03 Tetrahedron Lett.）
  • Stereoselective Synthesis of an Optically Active Axially Chiral Lactam and Its Reaction with Some Electrophiles.（1999/02 Tetrahedron Lett.）
  • Carbocyclization Reaction of Active Methine Compounds with Unactivated Alkenyl or Alkynyl Groups mediated by TiCl4-Et3N.（1998/11 J. Org. Chem.）
  • Intramolecular Carbotitanation Reaction of Active Methine Compounds Having an Unactivated Alkyne Mediated by TiCl4-Et3N.（1998/09 Tetrahedron Lett.）
  • ハロ環化中間体形成を活性化手法として用いる有機合成反応の開発（1998/08 有機合成化学協会誌）
  • t-BuOK-mediated Iodoaziridination Reaction of N-Allylic Tosylamide Derivatives.（1998/05 J. Org. Chem.）
  • Optically Active Axially Chiral Anilide and Maleimide Derivatives as New Chiral Reagents: Synthesis and Application to Asymmetric Diels-Alder Reaction.（1998/03 J. Org. Chem.）
  • NaH-mediated Iodoaziridination Reaction of N-Allylic Tosylamides.（1997/11 Tetrahedron Lett）
  • Catalytic Asymmetric Iodocarbocyclization Reaction of 4-Alkenylmalonates and Its Application to Enantiotopic Group Selective Reaction.（1997/10 J. Org. Chem.）
  • Regiocontrolled Iodoaminocyclization Reaction of an Ambident Nucleophile Mediated by Basic Metallic Reagent.（1997/10 J. Org. Chem.）
  • An Efficient Synthesis of Optically Active Axially Chiral Anilide and Its Application to Iodine-mediated Asymmetric Diels-Alder Reaction.（1997/06 Tetrahedron Lett.）
  • Diastereoselective -Iodination Reaction of 4-Alkenylamide Having a -Chiral Center.（1997/05 Tetrahedron）
  • Regio-contorolled Iodoaminocyclization Reaction of an Ambident Nucleophile Mediated by LiAl(Ot-Bu)4.（1997/02 Tetrahedron Lett）
  • Beckmann Rearrangement of O-4-Pentenyl Oxime through N-Bromosuccinimide-mediated Activating Process.（1997/01 Chem. Pharm. Bull.）
  • Diastereoselective Iodocarbocyclization Reaction of 2- or 3-Oxy-4-pentenylmalonate Derivatives.（1996/10 J. Org. Chem.）
  • Iodocarbocyclization Reaction.（1996/08 ）
  • A Mild Method for Generation of p-Methoxybenzyl Cation through NIS-mediated Activation of p-Methoxybenzyl 4-Pentenyl Ether.（1996/07 Tetrahedron）
  • Catalytic Asymmetric Iodocarbocyclization Reaction.（1995/12 Tetrahedron Lett.）
  • Structual Analysis of -Turn Mimics Containing a Substituted 6-Aminocaproic Acid Linker.（1995/10 J. Am. Chem. Soc.）
  • ヨードカルボ環化反応（1995/09 有機合成化学協会誌）
  • A Mild and Highly Chemoselective -Iodination of N-Allylic Carboxamides and Lactams.（1995/08 J. Org. Chem.）
  • Diastereoselective Iodocarbocyclization Reaction of 8-Phenylmenthyl Allylmalonate: An Efficient Preparation of a Synthetic Intermediate of Cyclopropane Amino Acids.（1995/03 Tetrahedron: Asymmetry）
  • Enantioselective Iodocarbocyclization of 4-Alkenylmalonate Derivatives Using a Chiral Titanium Complex.（1995/02 Tetrahedron Lett.）
  • Diels-Alder Reaction of N-Allylic Enamides and Lactam Derivatives through Iodine-mediated Activation.（1995/02 Tetrahedron Lett.）
  • Diastereoselective Iodocarbocyclization of 4-Pentenylmalonate Derivatives: Application to Cyclosarkomycin Synthesis.（1994/03 Tetrahedron Lett.）
  • Ionic Iodocarbocyclization Reactions of 4-Alkenyl- and 4-Alkynylmalonate Derivatives.（1993/03 J. Org. Chem.）
  • Asymetric Synthesis of -Amino Acids through -Iodination of Chiral Unsaturated Carboxamides and Stereoselective Iodolactonization.（1993/03 Tetrahedron Lett.）
  • Enantioselective Halocyclization Reaction using a Chiral Titanium Complex.（1992/05 Chem. Commun.）
  • Ionic Iodocarbocyclization Reaction.（1992/03 Tetrahedron Lett）
  • A Facile -Iodination Reaction of Unsaturated Amides.（1992/02 Tetrahedron Lett.）
  • Effect of Ti(Oi-Pr)4 on Stereoselectiviy of Halocyclization of 2-Substituted 4-Pentenoic Acid and 4-Penten-1-ol.（1991/01 Chem. Lett.）
  • Michael Addition of 2,2-Difluoroketene Silyl Acetal. Preparation of 4,4-Difluoroglutamic Acid and 5,5-Difluorolysine.（1990/08 Chem. Lett.）
  • Atom-transfer Reaction of Difluoroiodoacetate.（1990/06 Chem. Lett.）
  • (Methyl difluoroacetate)copper Reagent. Remarkable Solvent Effect on the 19F-NMR Spectrum, Stability and Reactivity.（1989/03 Chem. Lett.）
  • Synthesis of 3,3-Difluoro-2-Azetidinones and 2,3-Dideoxy-2,2-difluoro-3-aminosugars through the Reformatsky Reaction of Difluoroacetate with Imine.（1988/10 Tetrahedron Lett.）
  • Aldol Reaction of Iododifluoroacetate-Zn and 2,2-Difluoroketene Silyl Acetal.（1988/04 Tetrahedron Lett.）
  • Synthesis of 2,2-Difluoroesters by Iododifluoroacetate-Copper with Organic Halides.（1986/11 Tetrahedron Lett.）
  • Synthesis of -Difluorocarboxylic Acid Derivatives through the Claisen Rearrangement of 1,1-Difluoro-1-alkane-3-ols.（1985/11 Chem. Pharm. Bull.）
  • Synthesis of Trifuluoromethylated Sugars through the Aldol Reaction of 2-Trimethylsiloxy-4-trifluoromethylfuran.（1985/10 Chem. Pharm. Bull.）
  • Synthesis and Regioselective Substitution Reaction of 3-Trifluoromethylfuran.（1985/09 Chem. Pharm. Bull.）