Multipoint-Immobilized Ligands for Controlling Structures of Metal Complexes and Their Catalytic Performances

• Project/Area Number: 23850001
• Research Category: Grant-in-Aid for Research Activity Start-up
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: IWAI Tomohiro 北海道大学, 大学院・理学研究院, 助教 (30610729)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2012: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2011: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 触媒有機化学 / 多点固定化 / シリカゲル / ホスフィン / 遷移金属錯体触媒 / 不活性結合活性化 / 有機ホウ素化合物 / カップリング反応 / 不均一系触媒 / パラジウム / イリジウム / C-H活性化 / リン配位子 / ロジウム / C-H結合活性化 / ホウ素 / 塩化アリール

Research Abstract

A silica-tripod-supported triarylphosphine (Silica-3p-TPP) was synthesized and characterized structurally using solid-state NMR analysis. The tripodal immobilization constrained the mobility of the phosphine molecule efficiently, directing its P lone pair upward. This resulted in selective formation of a 1:1 metal-phosphine species that was free from unfavorable steric repulsions caused by the surface. The silica-supported tripod phosphine showed excellent ligand performances for transition metal catalyzed transformations of unreactive bonds.

Research Products

• [Journal Article] Synthesis of Primary and Secondary Alkylboronates through Site-Selective C(sp^3)-H Activation with Silica-Supported Monophosphine-Ir Catalysts. (2013)
  • Author(s): 川守田 創一郎
  • Journal Title: Journal of American Chemical Society Volume: 135 Issue: 8 Pages: 2947-2950
  • DOI: 10.1021/ja3126239
  • Peer Reviewed
• [Journal Article] Construction of Eight-Membered Carbocycles through Gold Catalysis with Acetylene-Tethered Silyl Enol Ethers (2013)
  • Author(s): Tomohiro Iwai, Hiori Okochi, Hideto Ito, Masaya Sawamura
  • Journal Title: Angew, Chem. Int. Ed. Volume: 52 Issue: 15 Pages: 4239-4242
  • DOI: 10.1002/anie.201300265
  • Peer Reviewed
• [Journal Article] 7,7,8,8-Tetraaryl-o-quinodimethane Stabilized by Dibenzo Annulation : A Helical π-Electron System That Exhibits Electrochromic and Unique Chiroptical Properties (2013)
  • Author(s): Takanori Suzuki, et al.
  • Journal Title: Chemistry-A European Journal Volume: 19 Issue: 1 Pages: 117-123
  • DOI: 10.1002/chem.201203092
  • Peer Reviewed
• [Journal Article] Conjugate Reduction of a,β-Unsaturated Carbonyl and Carboxyl Compounds with Poly(methylhydrosiloxane) Catalyzed by a Silica-Supported Compact phosphane-Copper Complex (2012)
  • Author(s): 川守田 創一郎
  • Journal Title: Advanced Synthesis & Catalysis Volume: 354 Issue: 18 Pages: 3440-3444
  • DOI: 10.1002/adsc.201200555
  • Peer Reviewed
• [Journal Article] Rh-Catalyzed Borylation of N-Adjacent C(sp^3)-H Bonds with a Silica-Supported Triarylphosphine Ligands (2012)
  • Author(s): Soichiro Kawamorita, Tatsuya Miyazaki, Tomohiro Iwai, Hirohisa Ohmiya, Masaya, Sawamura.
  • Journal Title: J.Am. Chem. Soc. Volume: 134 Issue: 31 Pages: 12924-12927
  • DOI: 10.1021/ja305694r
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Reduction of Acid Chlorides to Aldehydes with Hydrosilanes (2012)
  • Author(s): Tetsuaki Fujihara
  • Journal Title: Synlett Volume: 23 Issue: 16 Pages: 2389-2392
  • DOI: 10.1055/s-0032-1317155
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Esterification of Aryl Halides Using Aryl Formates without the Use of External Carbon Monoxide (2012)
  • Author(s): T. Fujihara, T. Hosoki, Y. Katafuchi, T. Iwai, J. Terao, Y. Tsuji
  • Journal Title: Chem. Commun. Volume: 48 Issue: 64 Pages: 8012-8014
  • DOI: 10.1039/c2cc33944g
  • NAID: 120005298241
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Addition of Aroyl Chlorides and Aliphatic Acid Chlorides to Terminal Alkynes (2012)
  • Author(s): Iwai, T. ; Fujihara, T. ; Terao, J. ; Tsuji, Y.
  • Journal Title: J.Am.Chem.Soc. Volume: 134 Issue: 2 Pages: 1268-1274
  • DOI: 10.1021/ja209679c
  • Peer Reviewed
• [Journal Article] Rh-Catalyzed Ortho-Selective C-H Borylation of N-Functionalized Arenes with Silica-Supported Bridgehead Monophosphine Ligands (2011)
  • Author(s): 川守田創一郎
  • Journal Title: Journal of American Chemical Society Volume: 133 Issue: 48 Pages: 19310-19313
  • DOI: 10.1021/ja208364a
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Borylation of Sterically Demanding Aryl Halides with Silica-Supported Compact Phosphane Ligand (2011)
  • Author(s): 川守田創一郎
  • Journal Title: Angewante Chemie, International Edition Volume: 50 Issue: 36 Pages: 8363-8366
  • DOI: 10.1002/anie.201103224
  • Peer Reviewed
• [Presentation] シリカ三脚担持型ホスフィンの合成と構造解析 (2013)
  • Author(s): 岩井智弘、田中遼太郎、原田友哉、澤村正也
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学,草津市
• [Presentation] リン酸型アニオン性官能基を有する光学活性含窒素複素環カルベンの合成と銅触媒不斉共役付加反応への応用 (2013)
  • Author(s): 秋山 裕樹
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこ・くさつキャンパス
• [Presentation] シリカ坦持かご型ホスフィン-イリジウム触媒によるキノリン誘導体の位置選択的C-H結合直接ホウ素化反応 (2013)
  • Author(s): 小西 菖太
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこ・くさつキャンパス
• [Presentation] シリカ坦持かご型ホスフィン-イリジウム触媒による不活性C(sp3)-H結合の直接ホウ素化反応 (2013)
  • Author(s): 村上 遼
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこ・くさつキャンパス
• [Presentation] シリカ三脚坦持型ホスフィンの合成と構造解析: 触媒的C(sp3)-H結合ホウ素反応への応用 (2013)
  • Author(s): 岩井 智弘
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこ・くさつキャンパス
• [Presentation] シリカ三脚担持型ホスフィン-パラジウム触媒による塩化アリール類のクロスカップリング反応 (2013)
  • Author(s): 田中 遼太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこ・くさつキャンパス
• [Presentation] ポリスチレン三脚架橋型ホスフィンの設計・合成と遷移金属触媒によるC-HおよびC-Cl結合変換反応への応用 (2013)
  • Author(s): 原田 友哉
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこ・くさつキャンパス
• [Presentation] Silica-Supported Tripod Triarylphophines: Synthesis and Use for Preparation of Highly Active Pd Catalysts Enabling Room Temperature Cross-Coupling Reactions of Chloroarenes (2012)
  • Author(s): Tomohiro Iwai, Ryotaro Tanaka, TomoyaHarada, Masaya Sawamura
  • Organizer: IKCOC-12
  • Place of Presentation: Rihga RoyalHotel, Kyoto
• [Presentation] Construction of Medium-Sized Rings through Gold-Catalyzed Cyclizations of Acetylenic Silyl Enol Ethers: Impact ofLigand Cavity Sizes (2012)
  • Author(s): Tomohiro Iwai, HioriOkochi, Hideto Ito, Masaya Sawamura
  • Organizer: GOLD 2012
  • Place of Presentation: Keio Plaza Hotel, Tokyo
• [Presentation] Iridium-Catalyzed Additions of Acid Chlorides to Alkynes withoutDecarbonylation (2012)
  • Author(s): Tomohiro Iwai
  • Organizer: Reaxys PhD Prize 2012 Symposium
  • Place of Presentation: Philadelphia, USA
• [Presentation] C-H/C-Cl Borylation Catalyzed by Transition-Metal Complexes with Silica-Supported Caged Phosphines (2012)
  • Author(s): Tomohiro Iwai, Soichiro Kawamorita, Tatsuya Miyazaki, Hirohisa Ohmiya, Masaya Sawamura
  • Organizer: The 5th GCOE International Symposium~Catalysis as the Basis for the Innovation in Materials Science~
  • Place of Presentation: Hokkaido University, Sapporo
• [Presentation] Site Selective Borylation of Unactivated Internal C(sp3)-H Bonds Catalyzed by Rh or Ir Complexes with Silica-Supported Monophoshine Ligands (2012)
  • Author(s): Masaya Sawamura
  • Organizer: The 7th International Conference on Cutting-Edge Organic Chemistry in Asia
  • Place of Presentation: Nanyang Technological University, Singapore
• [Presentation] Rh- or Ir-Catalyzed N-Directed Borylation of Unactivated C(sp3)-H Bonds with Silica-Supported Monophoshine Ligands (2012)
  • Author(s): Soichiro Kawamorita
  • Organizer: The Twelfth International Kyoto Conference on New Aspect of Organic Chemistry (IKCOC-12)
  • Place of Presentation: Rihga Royal Hotel KYOTO
• [Presentation] Silica-Supported Tripod Triarylphosphines: Synthesis and Use for Preparation of Highly Active Pd Catalysts Enabling Room Temperature Cross-Coupling Reactions of Chloroarenes (2012)
  • Author(s): Tomohiro Iwai
  • Organizer: The Twelfth International Kyoto Conference on New Aspect of Organic Chemistry (IKCOC-12)
  • Place of Presentation: Rihga Royal Hotel KYOTO
• [Presentation] シリカ担持トリアリールホスフィン-Rh触媒による窒素隣接C(sp3)－H結合のホウ素化反応 (2012)
  • Author(s): 川守田 創一郎
  • Organizer: 第59回有機金属化学討論会
  • Place of Presentation: 大阪大学 吹田キャンパス
• [Presentation] RH-CATALYZED DIRECT BORYLATION OF N-ADJACENT C(SP3)-H BONDS WITH SILICA-SUPPORTED CAGE-TYPE TRIARYL MONODENTATE PHOSPHINE LIGAND (2012)
  • Author(s): Soichiro Kawamorita
  • Organizer: XXV International Conference on Organometallic Chemistry (ICOMC 2012)
  • Place of Presentation: Lisbon University, Portugal
• [Presentation] Construction of Medium-Sized Rings through Gold-Catalyzed Cyclizations of Acetylenic Silyl Enol Ethers: Impact of Ligand Cavity Sizes (2012)
  • Author(s): Tomohiro Iwai
  • Organizer: The 6th International Conference on Gold Science Technology and its Applications (GOLD 2012)
  • Place of Presentation: Keio Plaza Hotel, Tokyo
• [Presentation] Iridium-Catalyzed Additions of Acid Chlorides to Alkynes without Decarbonylation (2012)
  • Author(s): Tomohiro Iwai
  • Organizer: 244th American Chemical Society Meeting, Reaxys PhD Prize 2012 Symposium
  • Place of Presentation: Pennsylvania Convention Center, Philadelphia, USA
  • Invited
• [Presentation] 半中空トリエチニルホスフィン-金触媒によるスルホンアミドのアルキンへの分子内付加反応:含窒素7員環化合物の合成 (2012)
  • Author(s): 原田友哉・伊藤英人・大宮寛久・岩井智弘・澤村正也
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学(横浜市)
• [Presentation] 異なるキャビティーサイズを有する半中空トリエチニルホスフィンの設計と合成:金触媒環化反応への応用 (2012)
  • Author(s): 大河内妃織・伊藤英人・岩井智弘・大宮寛久・澤村正也
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学(横浜市)
• [Presentation] Silica-SMAP触媒による芳香族C-ClおよびC-H結合の活性化-ホウ素化反応 (2012)
  • Author(s): 川守田創一郎・大宮寛久・岩井智弘・澤村正也
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学(横浜市)
• [Presentation] シリカゲル担持かご型トリアリールホスフィンーRh触媒によるN隣接sp3C-Hの直接ホウ素化反応 (2012)
  • Author(s): 宮崎辰也・川守田創一郎・大宮寛久・岩井智弘・澤村正也
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学(横浜市)
• [Presentation] 新規半中空トリエチニルホスフィン配位子の合成と金触媒アルキン環化反応への応用 (2012)
  • Author(s): 大河内妃織・伊藤英人, 岩井智弘, 澤村正也
  • Organizer: 化学系学協会北海道支部2012年冬季研究発表会
  • Place of Presentation: 北海道大学(札幌市)
• [Presentation] Ortho-Selective C-H Borylation of Functionalized Arenes Catalyzed by a Silica-Immobilized Compact Phosphine-Metal Complexes (2012)
  • Author(s): Kawamorita, S. :Ohmiya, H. ; Iwai, T. ; Sawamura, M.
  • Organizer: CRC International symposium on Green & sustainable Catalysis : from Theoretical and Fundamental Aspects to Catalvst Design
  • Place of Presentation: 北海道大学(札幌市)
• [Presentation] 遷移金属錯体による触媒的官能基化-高効率分子変換を目指して (2011)
  • Author(s): 岩井智弘
  • Organizer: 若手研究者のための有機化学札幌セミ ナー
  • Place of Presentation: 北海道大学, 札幌市
  • Year and Date: 2011-11-28
• [Presentation] 遷移金属錯体による触媒的官能基化-高効率分子変換を目指して (2011)
  • Author(s): 岩井智弘
  • Organizer: 若手研究者のための有機化学札幌セミナー
  • Place of Presentation: 北海道大学(札幌市)(招待講演)
  • Year and Date: 2011-11-28
• [Presentation] Directed Ortho Borylation of Functionalized Arenes Catalyzed by a Silica-Supported Bridgehead Phosphine-Metal Complexes (2011)
  • Author(s): Kawamorita, S. : Ohmiya, H.: Iwai, T. : Sawamura, M.
  • Organizer: The 1st Junior International Conference on Cutting-Edge Organic Chemistry in Asia
  • Place of Presentation: 廈門大学(中国)
• [Presentation] シリカ担持かご型ホスフィン配位子-ロジウム錯体による窒素官能性芳香族化合物のオルト位ホウ素化反応 (2011)
  • Author(s): 川守田創一郎・宮崎辰也・大宮寛久・岩井智弘・澤村正也
  • Organizer: 第108回触媒討論会
  • Place of Presentation: 北見工業大学(北見市)
• [Presentation] シリカ担持かご型ホスフィンの配位子効果に基づく芳香族C-H/C-Clの触媒的ホウ素化反応 (2011)
  • Author(s): 川守田創一郎・宮崎辰也・大宮寛久・岩井智弘・澤村正也
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学(名古屋市)
• [Remarks]
  • URL: http://wwwchem.sci.hokudai.ac.jp/~orgmet/
• [Remarks] 澤村研究室 北海道大学
  • URL: http://wwwchem.sci.hokudai.ac.jp/~orgmet/
• [Patent(Industrial Property Rights)] 有機高分子三点架橋型ホスフィン、そ れを配位子とする遷移金属錯体および触媒 (2013)
  • Inventor(s): 澤村正也、岩井智弘、原田友哉
  • Industrial Property Rights Holder: 国立大学法人北海道大学
  • Industrial Property Number: 2013-045650
  • Filing Date: 2013-03-07
• [Patent(Industrial Property Rights)] 有機高分子三点架橋型ホスフィン、それを配位子とする遷移金属錯体および触媒 (2013)
  • Inventor(s): 澤村正也、岩井智弘、原田友哉
  • Industrial Property Rights Holder: 澤村正也、岩井智弘、原田友哉
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2013-045650
  • Filing Date: 2013-03-07