Development of Reactions Catalyzed by Molybdenum Complexes with π-Ligands

• Project/Area Number: 19590021
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Nigata University of Phermacy and Applied Life Sciences
• Principal Investigator: SUGIHARA Takumichi Nigata University of Phermacy and Applied Life Sciences, 薬学部, 教授 (40222054)
• Project Period (FY): 2007 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2009: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2008: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2007: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: モリブデン / π-型配位子 / プロパルギル / ハロゲン化 / 触媒反応 / π型配位子

Research Abstract

We developed a couple of novel and efficient molybdenum-catalyzed reactions based on nature of π-type ligand which acted as both activation and stabilization of real catalytic species by the presence of equilibrium between σ- and π-type ligands. Our major findings were the follows ; 1) catalytic and nucleophilic substitution of allyl ethers by bromide ions delivered by molybdenum, 2) effect of π-propargyl ligands with various substituents on molybdenum to their catalytic activity, 3) cyclization of diynes catalyzed by molybdenum π-ligand complexes.

Research Products

• [Journal Article] Bromine-Transfer Reaciton from Propargyl to Allenylmethyl Groups Catalyzed by Molybdenum Hexacarbonyl (2010)
  • Author(s): T. Sugihara, Y. Tomizawa, Y. Shimizu
  • Journal Title: Heterocycles in press
• [Journal Article] α-Oxidation of Protected Secondary Amines by Bis(trichloroethyl)Azodicarboxylates (2010)
  • Author(s): T.Sugihara, 他
  • Journal Title: Heterocycles 82(印刷中)
  • Peer Reviewed
• [Journal Article] Efficient Synthesis of [2]Rotaxanes Based on Sequential Acetylene-Dicobalt Hexacarbonyl Complexation and Stopper Modification (2009)
  • Author(s): T. Sugihara, 他
  • Journal Title: Heterocycles 77 Pages: 1045-1056
  • Peer Reviewed
• [Journal Article] Substitution of Allenylmethyl Acetate by Halogens Derived from Propargyl Halides Catalyzed by Molybdenum Hexacarbonyl
  • Author(s): T. Sugihara, Y. Tomizawa, Y. Shimizu, S. Honzawa
  • Journal Title: Tetrahedron Lett. (印刷中)
  • Peer Reviewed
• [Presentation] ハロゲンと金属の不思議な関係 (2010)
  • Author(s): 杉原多公通
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山
  • Year and Date: 2010-03-30
• [Presentation] ハロゲンと金属の不思議な関係:新規ハロゲン化合物合成反応の提案 (2010)
  • Author(s): 杉原多公通
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山
• [Presentation] 触媒的ハロゲン置換反応の開発 (2009)
  • Author(s): 貝沼悠, 高村優太, 小林達朗, 本澤忍, 杉原多公通
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
• [Presentation] 加訂加に生成したπ-プロパルギルモリブデン錯体の反応に関する検討 (2009)
  • Author(s): 高村優太, 貝沼悠, 小林達郎, 本澤忍, 杉原多公通
  • Organizer: 第26回有機合成化学セミナー
  • Place of Presentation: 前橋
• [Presentation] モリブデン触媒によるハロゲン化合物合成反応の開発 (2008)
  • Author(s): 杉原多公通, 他
  • Organizer: 第56回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 新潟大学
  • Year and Date: 2008-11-30
• [Presentation] Molybdenum-Catalyzed Delivery of Halogens from Propargyl Halides to Compounds with Carbon-Carbon Multiple Bonds (2008)
  • Author(s): T. Sugihara, 他
  • Organizer: 第55回有機金属討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-30
• [Presentation] 『非常識』反応の開発 (2008)
  • Author(s): 杉原多公通
  • Organizer: 第3回21世紀おける薬物開発シンポジウム
  • Place of Presentation: 仙台
  • Year and Date: 2008-05-31
• [Presentation] Molybdenum-Catalyzed Reactions of Carbon-Carbon Multiple Bonds with Allyl and Propargyl Bromides (2008)
  • Author(s): 富澤恭子, 本澤忍, 杉原多公通
  • Organizer: 14^<th> IUPAC Symposium on Organometallic Chemistr directed towards Organic Synthesis
  • Place of Presentation: Kyoto
• [Presentation] モリブデンーハロゲン化プロパルギル系によるハロゲン化反応の開発 (2008)
  • Author(s): 富澤恭子, 清水悠司, 小林達朗, 本澤忍, 杉原多公通
  • Organizer: 第52回有機金属討論会
  • Place of Presentation: 大阪
• [Presentation] モリブデン触媒によるハロゲン化合物合成反応の開発 (2008)
  • Author(s): 貝沼悠, 高村優太, 小林達朗, 本澤忍, 杉原多公通
  • Organizer: 第56回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 新潟
• [Presentation] モリブデン触媒反応における臭素配位子の役割 (2007)
  • Author(s): 清水悠司, 富澤恭子, 本澤忍, 杉原多公通
  • Organizer: 第51回日本薬学会関東支部大会
  • Place of Presentation: 東京(星薬科大学)
  • Year and Date: 2007-10-05
• [Book] ブルース 有機化学 (2009)
  • Author(s): P.Y.Bruice, 大船泰史, 香月勗, 西郷和彦, 富岡清
  • Total Pages: 131
  • Publisher: 化学同人
• [Book] ベーシック薬学教科書シリーズ5有機化学 (2008)
  • Author(s): 夏苅英昭, 高橋秀依
  • Publisher: 化学同人
• [Book] 化学フロンティア19(有機遷移金属クラスター触媒反応) (2007)
  • Author(s): 杉原多公通
  • Publisher: 化学同人
• [Book] ブルース有機化学
  • Author(s): 杉原多公通
  • Total Pages: 150
  • Publisher: 化学同人(印刷中)
• [Remarks] ホームページ等
  • URL: http://www.taku-lab.com/