Development of New Molecular Transformations Based on Transition-Metal Catalyzed Cyanoboration of Carbon-Carbon Multiple Bonds

• Project/Area Number: 17065012
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: SUGINOME Michinori Kyoto University, 大学院・工学研究科, 教授 (60252483)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥26,600,000 (Direct Cost: ¥26,600,000); Fiscal Year 2008: ¥7,600,000 (Direct Cost: ¥7,600,000); Fiscal Year 2007: ¥7,600,000 (Direct Cost: ¥7,600,000); Fiscal Year 2006: ¥7,600,000 (Direct Cost: ¥7,600,000); Fiscal Year 2005: ¥3,800,000 (Direct Cost: ¥3,800,000)
• Keywords: 有機合成化学 / 触媒的ホウ素化 / シアノホウ素化 / クロスカップリング / レトロアリル化 / カルボホウ素化 / パラジウム触媒 / ニッケル触媒 / 立体相補的合成 / シアノボラン / 付加反応 / アルキニルボラン / 遷移金属触媒 / ホウ素化合物 / 反応機構 / α,β-不飽和ニトリル / クロロボラン / アルキニルホウ素化

Research Abstract

高度に官能基化された有機ホウ素化合物の新しい合成法として,炭素置換基とホウ素置換基を不飽和有機化合物に同時に付加させる触媒反応であるカルボホウ素化反応を開発した。炭素-ホウ素結合の触媒的活性化を鍵段階とする反応として,シアノボランを用いるシアノホウ素化およびアルキニルボランを用いるアルキニルホウ素化反応を確立した。また,クロロボランをホウ素置換基の供給源とし,有機金属化合物を有機置換基の供給源として用いるカルボホウ素化反応も開発した。この反応では塩素-ホウ素結合の触媒的活性化が鍵段階となることもわかった。

Research Products

• [Journal Article] Nickel-Catalyzed Ring-Opening Hydroacylation of Methylenecyclopropanes : Synthesis of γ,δ-Unsaturated Ketones from Aldehydes (2009)
  • Author(s): Taniguchi, H.; Ohmura, T.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 11298-11299
  • Peer Reviewed
• [Journal Article] Easily Attachable and Detachable ortho-Directing Agent for Arylboronic Acids in Ruthenium-Catalyzed Aromatic C-H Silylation (2009)
  • Author(s): Ihara, H.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 131(22) Pages: 7502-7503
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed, Regio- and Stereoselective Hydroalkynylation of Methylenecyclopropanes with Retention of the Cyclopropane Ring, Leading to the Synthesis of 1-Methyl-1-Alkynylcyclopropanes (2009)
  • Author(s): Shirakura, M.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 5060-5061
  • Peer Reviewed
• [Journal Article] Stereoselective Synthesis of cis-β-Methyl- and Phenyl-Substituted Alkenylboranes via Platinum-Catalyzed Dehydrogenative Borylation (2009)
  • Author(s): Ohmura, T.; Takasaki, Y; Suginome, M.
  • Journal Title: Angew. Chem., Int. Ed. 48 Pages: 2372-2375
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Intramolecular Cyanoboration of Allenes Leading to the Regioselective Synthesis of β-Cyanoallylboranes (2009)
  • Author(s): Yamamoto, A.; Ikeda, Y.; Suginome, M.
  • Journal Title: Tetrahedron Lett. 50 Pages: 5224-5226
  • Peer Reviewed
• [Journal Article] B(OMe)_3 as a Nonacidic Iminium Ion Generator in Mannich- and Ugi-type Reactions (2009)
  • Author(s): Tanaka, Y.; Hidaka, K.; Hasui, T.; Suginome, M.
  • Journal Title: Eur. J. Org. Chem. Pages: 1148-1151
  • Peer Reviewed
• [Journal Article] Synthesis of Masked Haloareneboronic Acids via Iridium-Catalyzed Aromatic C-H Borylation with 1,8-Naphthalenediaminatoborane (danBH) (2009)
  • Author(s): Iwadate, N.; Suginome, M.
  • Journal Title: J. Organomet. Chem. 694 Pages: 1713-1717
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed Regioselective Hydroalkynylation of Styrenes: Improved Catalyst System, Reaction Scope, and Mechanism (2009)
  • Author(s): Shirakura, M.; Suginome, M.
  • Journal Title: Org. Lett. 17(3) Pages: 523-526
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed intramolecular cyanoboration of allenes leading to the regioselective synthesis of β-cyanoallylboranes (2009)
  • Author(s): Michinori Suginome
  • Journal Title: Tetrahedron Lett. 50 Pages: 3168-3170
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Carboboration of Alkynes Using Chloroborane and Organozirconium Reagents (2008)
  • Author(s): Daini, M.; Suginome, M.
  • Journal Title: Chem. Commun. (41) Pages: 5224-5226
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed Addition of C-H Bonds of Terminal Alkynes to 1,3-Dienes and Styrenes (2008)
  • Author(s): Shirakura, M.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 130(16) Pages: 5410-5411
  • Peer Reviewed
• [Journal Article] Diarylborinic Acid Derivatives as a Catalytic Iminium Ion Generator in the Mannich-type Reaction Using sec-Amines, Aldehydes, and Ketene Silyl Acetals (2008)
  • Author(s): Tanaka, T.; Hasui, T.; Suginome, M.
  • Journal Title: Synlett (8) Pages: 1239-1242
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed trans- and cis-Carboboration of Alkynes Tethered to Chloroborane with Organozirconium Reagents: Ligand-Dependent Complementary Stereoselectivity (2008)
  • Author(s): Daini, M.; Yamamoto, A.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 2918-2919
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed cis- and trans-Silaboration of Terminal Alkynes: Complementary Access to Stereo-Defined Trisubstituted Alkenes (2008)
  • Author(s): Ohmura, T.; Oshima, K.; Suginome, M.
  • Journal Title: Chem. Commun. Pages: 1416-1418
  • Peer Reviewed
• [Journal Article] Synthetic Application of Intramolecular Cyanoboration on the Basis of Removal and Conversion of a Tethering Group by Palladium-Catalyzed Retro-allylation (2008)
  • Author(s): Ohmura, T.; Awano, T.; Suginome, M.; Yorimitsu, H.; Oshima, K.
  • Journal Title: Synlett (3) Pages: 423-427
  • NAID: 120001749568
  • Peer Reviewed
• [Journal Article] Silylboranes Bearing Dialkylamino Groups on Silicon as Silylene Equivalents: Palladium-Catalyzed Regioselective Synthesis of 2,4-Disubstituted Siloles (2008)
  • Author(s): Ohmura, T.; Masuda, K.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 130(5) Pages: 1526-1527
  • Peer Reviewed
• [Journal Article] A Mechanism for the Palladium-Catalyzed Regioselective Silaboration of Allene: A Theoretical Study (2008)
  • Author(s): Abe, Y.; Kuramoto, K.; Ehara, M.; Nakatsuji, H.; Suginome, M.; Murakami, M.; Ito, Y.
  • Journal Title: Organometallics 27 Pages: 1736-1742
  • Peer Reviewed
• [Journal Article] Differentially Protected Benzenediboronic Acids: Divalent Cross-Coupling Modules for the Efficient Synthesis of Boron-Substituted Oligoarenes (2008)
  • Author(s): Noguchi, H.; Shioda, T.; Chou, C. -M.; Suginome, M.
  • Journal Title: Org. Lett. 10(3) Pages: 377-380
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Carboboration of Alkynes Using Chloroborane and Organozir conium Reagents (2008)
  • Author(s): Michinori Suginome
  • Journal Title: Chem.Commun. Pages: 5224-5226
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed trans- and cis-Carboboration of Alkynes Tethered to Chloroborane with Organozirconium Reagents : Ligand-Dependent Complementary Stereoselectivity (2008)
  • Author(s): Michinori Suginome
  • Journal Title: J.Am.Chem.Soc. 130 Pages: 2918-2919
  • Peer Reviewed
• [Journal Article] Synthetic Application of Intramolecular Cyanoboration on the Basis of Removal and Conversion of a Tethering Group by Palladium-Catalyzed Retro-allylation (2008)
  • Author(s): Michinori Suginome
  • Journal Title: Synlett Pages: 423-427
  • NAID: 120001749568
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Asymmetric Silaborative C-C Cleavage of meso-Methylenecyclopropanes (2007)
  • Author(s): Ohmura, T.; Taniguchi, H.; Kondo, Y.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 129(12) Pages: 3518-3519
  • Peer Reviewed
• [Journal Article] Acid-free, Aminoborane-mediated Ugi-type Reaction Leading to General Utilization of Secondary Amines (2007)
  • Author(s): Tanaka, T.; Hasui, T.; Suginome, M.
  • Journal Title: Org. Lett. 9(22) Pages: 4407-4410
  • Peer Reviewed
• [Journal Article] Boron-Masking Strategy for the Selective Synthesis of Oligoarenes via Iterative Suzuki-Miyaura Coupling (2007)
  • Author(s): Noguchi, H.; Hojo, K.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 758-759
  • Peer Reviewed
• [Journal Article] Synthesis of Silylboronic Acid Esters Functionalized on Silicon (2007)
  • Author(s): Michinori Suginome
  • Journal Title: Organometallics 26 Pages: 1291-1294
• [Journal Article] Reductive Amination of Aldehydes Using Aminoboranes as Iminium Ion Generators (2006)
  • Author(s): Suginome, M.; Tanaka, M.; Hasui, T.
  • Journal Title: Synlett Pages: 1047-1050
  • Peer Reviewed
• [Journal Article] The Asymmetric Silaboration of Terminal Allenes Bearing a-Stereogenic Centers: Stereoselection Based on "Reagent Control (2006)
  • Author(s): Ohmura, T.; Suginome
  • Journal Title: M. Org. Lett. 8 Pages: 2503-2506
  • Peer Reviewed
• [Journal Article] Ligand-Controlled, Complementary Stereoselectivity in the Platinum-Catalyzed Intramolecular Silaboration of Alkenes" (2006)
  • Author(s): Ohmura, T.; Furukawa, H.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 13366-13367
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed Addition of Alkynylboranes to Alkynes (2006)
  • Author(s): Suginome, M.; Shirakura, M.; Yamamoto, A.
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 14438-14439
  • Peer Reviewed
• [Journal Article] Reactions of Cyanoboranes with a Palladium-PMe_3 Complex: Mechanism for the Catalytic Cyanoboration of Alkynes (2006)
  • Author(s): Suginome, M.; Yamamoto, A.; Sasaki, T.; Murakami M.
  • Journal Title: Organometallics 25 Pages: 2911-2913
  • Peer Reviewed
• [Journal Article] Aminoboranes as New Iminium Ion Generators in Amination Reactions (2006)
  • Author(s): Suginome, M.
  • Journal Title: Pure Appl. Chem. 78 Pages: 1377-1387
  • Peer Reviewed
• [Journal Article] Reactions of Cyanoboranes with a Palladium-PMe3 Complex: Mechanism for the Catalytic Cyanoboration of Alkynes (2006)
  • Author(s): Michinori Suginome
  • Journal Title: Organometallics 25 Pages: 2911-2913
• [Journal Article] Nickel-Catalyzed Addition of Alkynylboranes to Alkynes (2006)
  • Author(s): Michinori Suginome
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 14438-14439
• [Journal Article] Palladium-Catalyzed Asymmetric Silaboration of Allenes (2006)
  • Author(s): Michinori Suginome
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 13682-13683
• [Journal Article] Ligand-Controlled, Complementary Stereoselectivity in the Platinum-Catalyzed Intramolecular Silaboration of Alkenes (2006)
  • Author(s): Michinori Suginome
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 13366-13367
• [Journal Article] The Asymmetric Silaboration of Terminal Allenes Bearing α-Stereogenic Centers: Stereoselection Based on "Reagent Control" (2006)
  • Author(s): Michinori Suginome
  • Journal Title: Org. Lett. 8 Pages: 2503-2506
• [Journal Article] Palladium-Catalyzed Addition of Cyanoboranes to Alkynes Leading to Regio- and Stereoselective Synthesis of β-Boryl-α,β-unsaturated Nitriles (2005)
  • Author(s): Suginome, M.; Yamamoto, A.; Murakami, M.
  • Journal Title: Angew. Chem., Int. Ed. 44 Pages: 2380-2382
  • Peer Reviewed
• [Journal Article] Activation of Boron-Cyanide Bonds by Transition Metal Catalysts Leading to Intramolecular Cyanoboration of Alkynes (2005)
  • Author(s): Suginome, M.; Yamamoto, A.; Murakami, M.
  • Journal Title: J. Organomet. Chem. 690 Pages: 5300-5308
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed trans-Alkynylboration of Alkynes via Activation of a Boron-Chlorine Bond (2005)
  • Author(s): Yamamoto, A.; Suginome, M.
  • Journal Title: J. Am. Chem. Soc. 127 Pages: 15706-15707
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Addition of Cyanoboranes to Alkynes leading to Regio- and Stereoselective Synthesis of β-Boryl Nitriles (2005)
  • Author(s): M.Suginome 他2名
  • Journal Title: Angew.Chem.,Int.Ed. 44 Pages: 2380-2380
• [Journal Article] Activation of Boron-Cyanide Bonds by Transition Metal Catalysts Leading to Intramolecular Cyanoboration of Alkynes (2005)
  • Author(s): M.Suginome 他3名
  • Journal Title: J.Organomet.Chem. 690 Pages: 5300-5300
• [Journal Article] Nickel-Catalyzed trans-Alkynylboration of Alkynes via Activation of a Boron-Chlorine Bond (2005)
  • Author(s): A.Yamamoto 他1名
  • Journal Title: J.Am.Chem.Soc. 127 Pages: 15706-15706
• [Presentation] Oligo- and Polyarenes with Well-Defined Primary and Secondary Structures: New Synthetic Strategies and Functions (2009)
  • Author(s): Suginome, M.
  • Organizer: Catalysis and Fine Chemicals (C&FC)
  • Place of Presentation: Seoul, Korea(招待講演)
• [Presentation] New Catalytic Accesses to Functionalized Organoboronic Acids for Organic Synthesis (2009)
  • Author(s): Suginome, M.
  • Organizer: Nesmeyanov Conference
  • Place of Presentation: Moscow, Russia(招待講演)
• [Presentation] Protection of Boronyl Groups for the Synthesis of Functionalized Organoboronic Acid Derivatives (2009)
  • Author(s): Suginome, M.
  • Organizer: 5th BASF Boron Conference
  • Place of Presentation: Hyderabad, India(招待講演)
• [Presentation] Protection of Boronyl Groups for the Synthesis of Functionalized Organoboronic Acid Derivatives (2009)
  • Author(s): Michinori Suginome
  • Organizer: 5th BASF Boron Conference
  • Place of Presentation: Hyderabad, India
• [Presentation] 含ホウ素σ結合活性化に基づいた新触媒反応の開発 (2008)
  • Author(s): 杉野目道紀
  • Organizer: 東京農工大分子触媒セミナー「多元素間結合切断のための戦略と分子変換反応への新しい展開」
  • Place of Presentation: 東京(招待講演)
  • Year and Date: 2008-11-15
• [Presentation] Asymmetric Catalysis on Asymmetrically Synthesized Helical Polymers Bearing Metal-Binding Sites (2008)
  • Author(s): Michinori Suginome
  • Organizer: China-Japan Joint Symposium on the Element-Based Molecular Functions
  • Place of Presentation: Beijing, China
  • Year and Date: 2008-10-10
• [Presentation] Asymmetric Catalysis on Asymmetrically Synthesized Helical Polymers Bearing Metal-Binding Sites (2008)
  • Author(s): Michinori Suginome
  • Organizer: 20^<th> International Symposium on Chirality
  • Place of Presentation: Geneva, Switzerland
  • Year and Date: 2008-07-08
• [Presentation] 触媒的カルボホウ素化反応への取組みを起点とする新反応・新反応剤の開拓 (2008)
  • Author(s): 杉野目道紀
  • Organizer: 有機合成化学講習会
  • Place of Presentation: 東京(招待講演)
  • Year and Date: 2008-06-18
• [Presentation] Efficient Accesses to Organoboron Compounds for Organic Synthesis (2008)
  • Author(s): Suginome, M.
  • Organizer: China-Japan Joint Symposium on Functional Materials toward Future Catalysts
  • Place of Presentation: Beijing, China(招待講演)
  • Year and Date: 2008-01-16
• [Presentation] Efficient Accesses to Organoboron Compounds for Organic Synthesis (2008)
  • Author(s): Michinori Suginome
  • Organizer: China-Japan Joint Symposium on Functional Materials toward Future Catalysts
  • Place of Presentation: 北京(中国)
  • Year and Date: 2008-01-16
• [Presentation] Nickel-Catalyzed Addition of Alkyne C-H Bonds to 1,3-Dienes and Styrenes (2008)
  • Author(s): Suginome, M.
  • Organizer: 9th International Conference on Organic Reactions (ISOR)
  • Place of Presentation: Chiayi, Taiwan(招待講演)
• [Presentation] Boron-Masking Strategy for Selective Synthesis of Oligoareneboronic Acids via Cross-Coupling Reactions (2008)
  • Author(s): Suginome, M.
  • Organizer: 13th International Conference on Boron Chemistry (IMEBORON-XIII)
  • Place of Presentation: Platja d'Aro, Spain(招待講演)
• [Presentation] Asymmetric Catalysis on Asymmetrically Synthesized Helical Polymers Bearing Metal-Binding Sites (2008)
  • Author(s): Suginome, M.
  • Organizer: 20^<th> International Symposium on Chirality
  • Place of Presentation: Geneva, Switzerland(招待講演)
• [Presentation] (2008)
  • Author(s): Michinori Suginome
  • Organizer: 13th International Conference on Boron Chemistry (IMEBORON-XIII)
  • Place of Presentation: Platja d'Aro, Spain
• [Presentation] Nickel-Catalyzed Addition of Alkyne C-H Bonds to 1,3-Dienes and Styrenes (2008)
  • Author(s): Michinori Suginome
  • Organizer: 9th International Conference on Organic Reactions (ISOR-2008)
  • Place of Presentation: Chiayi, Taiwan
• [Presentation] ホウ素の特性を活かした新しい精密有機合成 (2007)
  • Author(s): 杉野目道紀
  • Organizer: 東京工業大学理学研究流動機構シンポジウム
  • Place of Presentation: 東京(招待講演)
  • Year and Date: 2007-11-30
• [Presentation] ホウ素化合物の「活性化」と「保護」を利用した精密有機合成 (2007)
  • Author(s): 杉野目道紀
  • Organizer: 2007年日本化学会西日本大会
  • Place of Presentation: 岡山(招待講演)
  • Year and Date: 2007-11-10
• [Presentation] ホウ素化合物の遷移金属触媒反応 (2006)
  • Author(s): 杉野目道紀
  • Organizer: 第3回九州大学理学研究院化学部門研究セミナー
  • Place of Presentation: 福岡(招待講演)
  • Year and Date: 2006-01-14
• [Presentation] New Boron-Based Reagents and Reactions for Organic Synthesis (2006)
  • Author(s): Suginome, M.
  • Organizer: 2nd International BASF Boron Conference
  • Place of Presentation: Tokyo(招待講演)
• [Presentation] Exploration of New Transition Metal Catalyzed Reactions for Organic Synthesis (2006)
  • Author(s): 杉野目道紀
  • Organizer: 有機合成化学セミナー
  • Place of Presentation: 大沼(受賞講演)
• [Book] Comprehensive Organometallic Chemistry III (2007)
  • Author(s): Suginome, M.
  • Total Pages: 869
  • Publisher: Elsevier
• [Book] Comprehensive Organometallic Chemistry III, Vol.10 (2007)
  • Author(s): Michinori Suginome(分担執筆)
  • Total Pages: 869
  • Publisher: Elsevier
• [Remarks]
  • URL: http://www.sbchem.kyoto-u.ac.jp/suginome-lab/
• [Remarks]
  • URL: http://www.sbchem.kyoto-u.ac.jp/suginome-lab/
• [Remarks]
  • URL: http://www.sbchem.kyoto-u.ac.jp/suginome-lab/
• [Patent(Industrial Property Rights)] クロスカップリング反応を用いたオリゴマー化合物の合成方法 (2007)
  • Inventor(s): 杉野目道紀, 野口宙幹, 北條浩章
  • Industrial Property Rights Holder: 国立大学法人京都大学
  • Industrial Property Number: 2008-505123
  • Filing Date: 2007-03-09