Asymmetric Catalytic Synthesis of Optically Active Organoboron Compounds with Chiral Borylcopper Species

2010 Fiscal Year Final Research Report

• Project/Area Number: 20350043
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: ITO Hajime Hokkaido University, 大学院・工学研究院, 教授 (90282300)
• Project Period (FY): 2008 – 2010
• Keywords: 不斉合成 / 合成化学 / 有機化学 / 触媒・化学プロセス / 銅

Research Abstract

Novel methods for efficient synthesis of optically active organoboron compounds with chiral copper(I)-catalyst have been developed. The reactions, which include copper(I) salts and chiral phosphine ligands, promote various borylation reaction to produce optically active organoboron compounds with high enantioselectivity. This method enables the asymmetric catalytic synthesis of unprecedented chiral cyclopropyl-, ally- and homoallyboronates, which will facilitate the synthesis of intermediates for medicines.

Research Products

• [Journal Article] Enantioselective Synthesis of trans-Aryl- and -Heteroaryl-Substituted Cyclopropylboronates by Copper(I)-Catalyzed Reactions of Allylic Phosphates with a Diboron Derivative (2010)
  • Author(s): Zhong C.; Kunii S.; Kosaka Y.; Sawamura M.; Ito H.
  • Journal Title: J. Am. Chem. Soc. 132 Pages: 11440
  • Peer Reviewed
• [Journal Article] Copper(I)-Catalyzed Asymmetric Monoborylation of 1,3-Dienes : Synthesis of Enantioenriched Cyclic Homoallyl- and Allylboronates (2010)
  • Author(s): Sasaki Y.; Zhong C.; Sawamura M.; Ito H.
  • Journal Title: J. Am. Chem. Soc. 132 Pages: 1226
  • Peer Reviewed
• [Journal Article] Stereospecific Synthesis of Cyclobutylboronates through Copper(I)-Catalyzed Reaction of Homoallylic Sulfonates and a Diboron Derivative (2010)
  • Author(s): Ito H.; Toyoda T.; Sawamura M.
  • Journal Title: J. Am. Chem. Soc. 132 Pages: 5990
  • Peer Reviewed
• [Journal Article] Desymmetrization of meso-2-Alkene-1,4-diol Derivatives through Copper(I)-Catalyzed Asymmetric Boryl Substitution and Stereoselective Allylation of Aldehydes (2010)
  • Author(s): Ito H.; Okura T.; Matsuura K.; Sawamura M.
  • Journal Title: Angew. Chem., Int. Ed. 49 Pages: 560
  • Peer Reviewed
• [Journal Article] Direct Enantio-Convergent Transformation of Racemic Ssubstrates without Racemization or Symmetrization (2010)
  • Author(s): Ito H.; Kunii S.; Sawamura M.
  • Journal Title: Nature Chemistry 2 Pages: 972
  • Peer Reviewed
• [Journal Article] The Synthesis of Allenes by Cu(I)-Catalyzed Regio- and Stereoselective Reduction of Propargylic Carbonates with Hydrosilanes (2009)
  • Author(s): Zhong C.; Sasaki Y.; Ito H.; Sawamura M.
  • Journal Title: Chem. Commun. Pages: 5850
  • Peer Reviewed
• [Journal Article] Gold(I) Hydride Intermediate in Catalysis : Dehydrogenative Alcohol Silylation Catalyzed by Gold(I) Complex (2009)
  • Author(s): Ito H.; Saito T.; Miyahara T.; Zhong C.; Sawamura, M.
  • Journal Title: Organometallics 28 Pages: 4829
  • Peer Reviewed
• [Journal Article] Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron : Selective Synthesis of Multisubstituted Allenylboronates (2008)
  • Author(s): Ito H.; Sasaki Y.; Sawamura M.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 15774
  • Peer Reviewed
• [Journal Article] Reversible Mechanochromic Luminescence of [(C_6F_5Au)_2(μ-1,4-diisocyanobenzene)] (2008)
  • Author(s): Ito H.; Saito T.; Oshima N.; Kitamura N.; Ishizaka S.; Hinatsu Y.; Wakeshima M.; Kato M.; Tsuge K.; Sawamura M.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 10044
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Boron-Silicon Bifunctional Cyclopropane Derivatives through Enantioselective Copper(I)-Catalyzed Reaction of Allylic Carbonates with a Diboron Derivative (2008)
  • Author(s): Ito H.; Kosaka Y.; Nonoyama K.; Sasaki Y.; Sawamura M.
  • Journal Title: Angew. Chem., Int. Ed. 47 Pages: 7424
  • Peer Reviewed
• [Presentation] Asymmetric synthesis of chiral organoboron compounds through copper(I) catalysis with diboron (2010)
  • Author(s): 伊藤肇
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-20
• [Presentation] 11 族金属触媒による有機ホウ素化合物の不斉合成反応 (2010)
  • Author(s): 伊藤肇
  • Organizer: 2010 年度 触媒学会北海道地区札幌講演会
  • Year and Date: 2010-12-03
• [Presentation] Cu(I)-catalyzed Asymmetric Synthesis of Organoboron Compounds (2010)
  • Author(s): 伊藤肇
  • Organizer: Catalytic Asymmetric Synthesis-2010
  • Place of Presentation: Beijing, China
  • Year and Date: 2010-05-19
• [Presentation] 11 族金属触媒のσ結合メタセシス反応を基軸とする合成反応 (2008)
  • Author(s): 伊藤肇
  • Organizer: 第25 回有機合成化学セミナー
  • Place of Presentation: 阿蘇市
  • Year and Date: 2008-09-08
• [Book] 使える!有機合成反応 241 実践ガイド(丸岡啓二,野崎京子,石井康敬,大寺純蔵,富岡清 編著) (2010)
  • Author(s): 澤村正也,伊藤肇
  • Total Pages: 314-315
  • Publisher: 化学同人
• [Remarks] ホームページ等
  • URL: http://labs.eng.hokudai.ac.jp/labo/organoelement/
• [Remarks] 新聞報道等
• [Remarks] 「光学活性化合物新合成法を開発」北海道新聞2010年8月30日
• [Remarks] 「ラセミ化合物から直接合成」化学工業日報2010年8月31日
• [Remarks] 「直接エナンチオ収束反応の開発」北海道医療新聞2010年12月10日
• [Remarks] 「北海道大学、医薬品などの開発に役立つ光学活性化合物の新合成法を開発」日経プレスリリース2010年8月30日