Preparation of Silyl Cation Species for Catalytic Asymmetric Synthesis

2008 Fiscal Year Final Research Report

• Project/Area Number: 19750069
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: HARA Kenji Hokkaido University, 触媒化学研究センター, 准教授 (10333593)
• Project Period (FY): 2007 – 2008
• Keywords: 触媒設計 / 反応

Research Abstract

本研究課題は、強力なルイス酸としての機能を有しながらも未開発であるケイ素カチオン種に着目し、その機能を不斉合成反応触媒として充分に発揮させるための独自の設計を施す手法の開発を目的とした。基本骨格を用いた合成経路の検証、分子集積触媒反応場の構築、メソポーラスシリカ表面上でのケイ素種の精密修飾手法の精査により精密な分子設計に基づいた効率的かつ特異な立体選択性を発現するケイ素カチオン種触媒を創成するための基礎的手法が確立した。

Research Products

• [Journal Article] Directed Ortho Borylation of Functionalized Arenes Catalyzed by a Silica-Supported Compact Phosphine-Iridium System (2009)
  • Author(s): Kawamorita, S., Ohmiya, H., Hara, K., Fukuoka, A. and Sawamura, M.
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 5058-5059
  • Peer Reviewed
• [Journal Article] Self-Assembled Monolayers of Compact Phosphanes with Alkanethiolate Pendant Groups: Remarkable Reusability and Substrate Selectivity in Rh Catalysis (2008)
  • Author(s): Hara, K., Akiyama, R., Takakusagi, S., Uosaki, K., Yoshino, T., Kagi, H. and Sawamura, M.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 5627-5630
  • Peer Reviewed
• [Journal Article] Hydrogenation of Hindered Ketones Catalyzed by a Silica-Supported Compact Phosphine System (2008)
  • Author(s): Kawamorita, S., Hamasaka, G., Ohmiya, H., Hara, K., Fukuoka, A. and Sawamura, M.
  • Journal Title: Org. Lett. 10 Pages: 4697-4700
  • Peer Reviewed
• [Journal Article] Synthesis, Properties and Catalytic Applications of Caged, Compact Trialkylphosphine 4-Phenyl-1-phospha-4-silabicyclo[2.2.2]octane (2008)
  • Author(s): Ochida, A., Hamasaka, G., Yamauchi, Y., Kawamorita, S., Ohshima, N., Hara, K., Ohmiya, H. and Sawamura, M.
  • Journal Title: Organometallics 27 Pages: 5494-5503
  • Peer Reviewed
• [Journal Article] Synthesis of Silica-Supported Compact Phosphines and Their Application to Rhodium-Catalyzed Hydrosilylation of Hindered Ketones with Triorganosilanes (2008)
  • Author(s): Hamasaka, G., Kawamorita, S., Ochida, A., Akiyama, R., Hara, K., Fukuoka, A., Asakura, K., Chun, W. J., Ohmiya, H. and Sawamura, M.
  • Journal Title: Organometallics 27 Pages: 6495-6506
  • Peer Reviewed
• [Presentation] 金表面上に形成したIr-ホスフィン錯体単分子層を触媒とするアルケンのヒドロホウ素化反応 (2009)
  • Author(s): 秋山龍人,原賢二,高見仁,魚崎浩平,福岡淳,澤村正也
  • Organizer: 日本化学会第89 春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] 金表面上に形成したRh-ホスフィン錯体単分子層を触媒とするアルキンおよびアルケンのヒドロシリル化反応 (2009)
  • Author(s): 秋山龍人,原賢二,石黒由利子,魚崎浩平,福岡淳,澤村正也
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] イソシアニド分子を用いた金表面上におけるロジウム錯体単分子層の形成 (2009)
  • Author(s): 梶義規,原賢二,福岡淳
  • Organizer: 日本化学会第89 春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] メソポーラスシリカ表面の精密有機修飾 (2009)
  • Author(s): 赤羽紗以子,原賢二,福岡淳
  • Organizer: 日本化学会第89 春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] Preparation and Catalytic Application of Densely Packed Self-assembled Monolayer of Phosphine-terminated Alkanethiolate on Gold Surface (2009)
  • Author(s): Hara, K.
  • Organizer: International Symposium for Environmental Innovation Driven by Chemistry and Catalytic Science
  • Place of Presentation: Sapporo
  • Year and Date: 20090318-19
• [Presentation] メソポーラスシリカ表面の精密有機修飾 (2009)
  • Author(s): 赤羽紗以子,原賢二,福岡淳
  • Organizer: 日本化学会北海道支部2009 年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 20090203-04
• [Presentation] 金表面上におけるイソシアニド単分子層を利用した精密触媒場の形成 (2009)
  • Author(s): 梶義規,原賢二,福岡淳
  • Organizer: 日本化学会北海道支部2009 年冬季研究発表会
  • Place of Presentation: 札幌
  • Year and Date: 20090000
• [Presentation] 金表面上に固定化した遷移金属錯体による触媒反応 (2009)
  • Author(s): 原賢二
  • Organizer: 日本化学会第89 春季年会特別企画「表面を舞台とする化学・物理・機能」
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-27
• [Presentation] 金表面におけるコンパクトなホスフィンの高密度単分子層-形成と触媒への応用- (2008)
  • Author(s): 原賢二
  • Organizer: 第28 回表面科学講演大会
  • Place of Presentation: 東京
  • Year and Date: 20081113-15
• [Presentation] 金表面上に形成したIr-かご型ホスフィン錯体単分子層を触媒とするアルケンのヒドロホウ素化反応 (2008)
  • Author(s): 秋山龍人,高見仁,原賢二,高草木達,魚崎浩平,福岡淳,澤村正也
  • Organizer: 第102 回触媒討論会
  • Place of Presentation: 名古屋
  • Year and Date: 20080923-26
• [Presentation] Self-Assembled Monolayer of Alkanethiolate on Gold Surface -Application to Catalysis- (2008)
  • Author(s): Hara, K., Akiyama, R., Takakusagi, S., Uosaki, K., Fukuoka, A., Sawamura, M.
  • Organizer: 22nd Conference of the European Colloid and Interface Society
  • Place of Presentation: Crakow, Poland
  • Year and Date: 20080831-0905
• [Presentation] 金表面上に形成したロジウム錯体単分子層の触媒機能 (2008)
  • Author(s): 原賢二
  • Organizer: 第48 回オーロラセミナー
  • Place of Presentation: 小樽
  • Year and Date: 20080809-10
• [Presentation] Monolayer of Rhodium-Phosphine Complex on Gold Surface: Reusable and Chemo-Selective Catalyst for Dehydrogenative Alcohol Silylation (2008)
  • Author(s): Hara, K., Akiyama, R., Takakusagi, S., Uosaki, K., Fukuoka, A., Sawamura, M.
  • Organizer: the International Symposium on Creation and Control of Advanced Selective Catalysis
  • Place of Presentation: Kyoto
  • Year and Date: 20080709-11
• [Presentation] Densely-Packed Self-Assembled Monolayer of Phosphine-Terminated Alkanetiolate on Gold Surface (2008)
  • Author(s): Hara, K.
  • Organizer: Joint Symposium of PCOSS, Xiamen Univ. and CRC, Hokkaido Univ.
  • Place of Presentation: Sapporo
  • Year and Date: 20080527-28