Development of Dehydrative S-Allylation toward Synthetic Biology

• Project/Area Number: 24655076
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: KITAMURA Masato 名古屋大学, 創薬科学研究科, 教授 (50169885)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: アリルアルコール / システイン / ペプチド修飾 / ルテニウム / アリル化 / 合成生物学 / S-アリル化

Research Abstract

S-Allylated cysteine and peptides show various biological activities. In order to efficient generate a series of chemical libraries, direct S-allylation of thiol-containing amino acid and peptides in the native form is favored. This ideal process has been firstly realized by use of our catalytic system consisting of either [CpRu(CH3CN)3]PF6 and 2-quinolinecarboxylic acid or the pai-allyl Ru complex. The S-allylation process even in aqueous media including an acetate buffer system with high reactivity and S-chemoselectivity, suggesting a possibility of application of the present method for cysteine-containing proteins. Various C(2)-substituted allyl alcohols can be utilized, paving a way to a new type of lipopeptide library

Research Products

• [Journal Article] (2013)
  • Author(s): Yamamura, T.; Nakatsuka, H.; Tanaka, S.; Kitamura, M.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 52 Pages: 9318-9315
• [Journal Article] (2013)
  • Author(s): Kitamura, M.; Miyata, K.; Seki, T.; Vatmurge, N.; Tanaka, S.
  • Journal Title: Pure Appl. Chem. Volume: 85 Pages: 1121-1132
• [Journal Article] Ferrocene, 1,1'-bis[(2R,4R)-2,4-diethyl-1-phosp hetanyl]-, stereoisomer; Ferrocene, 1,1'- bis[(2S,4S)-2,4-diethyl-1- phosphetanyl]-, stereoisomer, RN01622 (2013)
  • Author(s): 北村雅人
  • Journal Title: e-EROS
• [Journal Article] Asymmetric Hydrogenation of tert-Alkyl Ketones: DMSO Effect in Unification of Stereoisomeric Ruthenium Complexes (2013)
  • Author(s): Tomoya Yamamura, Hiroshi Nakatsuka, Shinji Tanaka, Masato Kitamura
  • Journal Title: Angewandte Chemie International Edition Volume: 52 Issue: 35 Pages: 9313-9315
  • DOI: 10.1002/anie.201304408
  • Peer Reviewed
• [Journal Article] CpRu-catalyzed asymmetric dehydrative allylation (2013)
  • Author(s): Masato Kitamura, Kengo Miyata, Tomoaki Seki, Namdev Vatmurge, Shinji Tanaka
  • Journal Title: Pure and Applied Chemistry Volume: 85 Issue: 6 Pages: 1121-1132
  • DOI: 10.1351/pac-con-12-10-02
  • Peer Reviewed
• [Journal Article] (2012)
  • Author(s): Xu, B-H.; Yanez, R. A. A.; Nakatsuka, H.; Kitamura, M.; Fröhlich, R.; Kehr, G.; Erker
  • Journal Title: Chem. Asian J. Volume: 7 Pages: 1347-1356
• [Journal Article] (2012)
  • Author(s): Nakatsuka, H.; Fröhlich, R.; Kitamura, M.; Kehr, G.; Erker, G.
  • Journal Title: Eur. J. Inorg. Chem Pages: 1163-1166
• [Journal Article] (2012)
  • Author(s): Miyata, K.; Kitamura, M.
  • Journal Title: Synthesis Volume: 44 Pages: 2138-2146
• [Journal Article] (2012)
  • Author(s): Seki, T.; Tanaka, S.; Kitamura, M.
  • Journal Title: Org. Lett. Volume: 14 Pages: 608-611
• [Journal Article] Reduction?Hydrogenation : C=C; Chemoselective (2012)
  • Author(s): 塚本眞幸、北村雅人
  • Journal Title: Comprehensive Chirality
• [Journal Article] Reaction of Frustrated Lewis Pairs with Ketones and Esters (2012)
  • Author(s): Bao-Hua Xu, Raul Alfonso Adler Yanez, Hiroshi Nakatsuka, Masato Kitamura, Roland Frohlich, Gerald Kehr, Gerhard Erker
  • Journal Title: Chemistry-An Asian Journal Volume: 7 Issue: 6 Pages: 1347-1356
  • DOI: 10.1002/asia.201100960
  • Peer Reviewed
• [Journal Article] Double Arylation of Acetylenedicarboxylate with B(C_6F_5)_3 (2012)
  • Author(s): Hiroshi Nakatsuka, Roland Frohlich, Masato Kitamura, Gerald Kehr, Gerhard Erker
  • Journal Title: European Journal of Inorganic Chemistry Volume: 8 Issue: 8 Pages: 1163-1166
  • DOI: 10.1002/ejic.201101413
  • Peer Reviewed
• [Journal Article] Asymmetric Dehydrative C-, N-, and O-Allylation Using Naph-diPIM-dioxoi-Pr-CpRu/p-TsOH Combined Catalyst (2012)
  • Author(s): K. Miyata, M. Kitamura
  • Journal Title: Synthesis Volume: 44 Issue: 14 Pages: 608-611
  • DOI: 10.1055/s-0031-1290301
  • Peer Reviewed
• [Journal Article] Enantioselective Synthesis of Pyrrolidine-, Piperidine-, and Azepane-type N-Heterocycles with α-Alkenyl Substitution : the CpRu-Catalyzed Dehydrative Intramolecular N-Allylation Approach (2012)
  • Author(s): Tomoaki Seki, Shinji Tanaka, Masato Kitamura
  • Journal Title: Organic Letters Volume: 14 Issue: 2 Pages: 608-611
  • DOI: 10.1021/ol203218d
  • Peer Reviewed
• [Presentation] 脱水型不斉Tsuji-Trost反応の開発 (2014)
  • Author(s): 北村雅人
  • Organizer: 集積化学成果報告会
  • Place of Presentation: 東京
  • Year and Date: 2014-01-25
• [Presentation] 脱水型不斉Tsuji-Trost反応の開発 (2014)
  • Author(s): 北村雅人
  • Organizer: 集積化学公開シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2014-01-24
• [Presentation] 脱水型不斉Tsuji-Trost反応の開発 (2014)
  • Author(s): 北村雅人
  • Organizer: 集積反応化学公開シンポジウム
  • Place of Presentation: 東京
• [Presentation] 脱水型不斉Tsuji-Trost反応の開発 (2014)
  • Author(s): 北村雅人
  • Organizer: 集積反応化学平成25年度第2回成果報告会
  • Place of Presentation: 東京
• [Presentation] 触媒的不斉水素化の開発・応用・機構解明 (2013)
  • Author(s): 北村雅人
  • Organizer: 平成25年有機合成化学後期(秋期)講習会
  • Place of Presentation: 東京
• [Presentation] Development of Magnetically Separable Heterogeneous Deallylation Catalyst (2013)
  • Author(s): 田中慎二、北村雅人
  • Organizer: The 16th International Symposium Relation Between Homogeneous and Heterogeneous Catalysis
  • Place of Presentation: 札幌
• [Presentation] 触媒的不斉水素化の開発・応用・機構解明 (2013)
  • Author(s): 北村雅人
  • Organizer: 平成25年度有機合成化学後期(秋期)講習会
  • Place of Presentation: 東京
  • Invited
• [Presentation] Development of Magnetically Separable Heterogeneous Deallylation Catalyst (2013)
  • Author(s): S. Tanaka, M. Kitamura
  • Organizer: The 16th International Symposium on Relations Between Homogeneous ond Heterogeneous Catalysis
  • Place of Presentation: Sapporo
• [Presentation] 脱水型不斉Tsuji-Trost反応 (2012)
  • Author(s): 北村雅人
  • Organizer: 第24回万有シンポジウム
  • Place of Presentation: 札幌
  • Year and Date: 2012-07-07
• [Presentation] 2001年ノーベル賞-右手型と左手型の分子を作り分ける- (2012)
  • Author(s): 北村雅人
  • Organizer: あいちサイエンスフェスティバル
  • Place of Presentation: 豊橋
  • Year and Date: 2012-06-09
• [Presentation] Design and Synthesis of Linear N4 Chiral Ligands : Its Application to Asymmetric Hydrogenation of Aromatic Ketones (2012)
  • Author(s): 吉村正宏、北村雅人
  • Organizer: Cambodian Malaysian Chemical Conference (CMCC) 2012
  • Place of Presentation: カンボジア
• [Presentation] CpRu-Catalyzed Dehydrative Allylation of Thiols and Application for Peptide Modification (2012)
  • Author(s): 田中慎二、北村雅人
  • Organizer: 17th Malaysian Chemical Congress
  • Place of Presentation: クアラルンプール
• [Presentation] A New Method for Lipidation of Cysteine-containing Peptide (2012)
  • Author(s): 田中慎二、Jaisankar, P.、北村雅人
  • Organizer: 第三回物質統合シンポジウム
  • Place of Presentation: 福岡
• [Presentation] CpRu-Catalyzed Asymmetric Dehydrative Allylation (2012)
  • Author(s): 北村雅人
  • Organizer: 19th International Conference on Organic Synthesis and 24th Royal Australian Institute Organic Conference
  • Place of Presentation: メルボルン
• [Presentation] A New sp^2N Bidentate Ligand (2012)
  • Author(s): 北村雅人
  • Organizer: The 2nd International Conference on Molecular and Functional Catalysis
  • Place of Presentation: シンガポール
• [Presentation] New Chiral sp^2N Bidentate Ligand; Naph-diPIM-dioxo-R-Donor-Acceptor Bifunctional Catalyst- (2012)
  • Author(s): 北村雅人
  • Organizer: The 6th Takeda Science Foundation Symposium on PharmaSciences
  • Place of Presentation: 大阪
• [Presentation] Design and Synthesis of Linear N4 Chiral Ligands: Its Application to Asymmetric Hydrogenation of Aromatic Ketones (2012)
  • Author(s): 吉村正宏・北村雅人
  • Organizer: Cambodian Malaysian Chemical Conference (CMCC) 2012
  • Place of Presentation: Angkor Century Resort & Spa, Siem Reap, Cambodia
  • Invited
• [Presentation] CpRu-Catalyzed Dehydrative Allylation of Thiols and Application for Peptide Modification. (2012)
  • Author(s): 田中慎二・北村雅人
  • Organizer: 17th Malaysian Chemical Congress
  • Place of Presentation: Kuala Lumpure, Malaysia
  • Invited
• [Presentation] A New Method for Lipidation of Cysteine-containing Peptides (2012)
  • Author(s): 田中慎二・Jaisankar,P.・北村雅人
  • Organizer: 第3回統合物質シンポジウム
  • Place of Presentation: 九州大学
  • Invited
• [Presentation] CpRu–Catalyzed Asymmetric Dehydrative Allylation (2012)
  • Author(s): 北村雅人
  • Organizer: 19th International Conference on Organic Synthesis and 24th Royal Australian Institute Organic Conference
  • Place of Presentation: Melbourne
  • Invited
• [Presentation] A New sp2N Bidentate Ligand (2012)
  • Author(s): 北村雅人
  • Organizer: The 2nd International Conference on Molecular and Functional Catalysis
  • Place of Presentation: Singapore
  • Invited
• [Presentation] New Chiral sp2N Bidentate Ligand: Naph-diPIM-dioxo-R ―Donor-Acceptor Bifunctional Catalyst― (2012)
  • Author(s): 北村雅人
  • Organizer: The 6th Takeda Science Foundation Symposium on PharmaSciences
  • Place of Presentation: Osaka
  • Invited
• [Presentation] 2001年ノーベル賞 ―右手型と左手型の分子をつくり分ける―
  • Author(s): 北村雅人
  • Organizer: あいちサイエンスフェスティバル
  • Place of Presentation: 豊橋
  • Invited
• [Presentation] 脱水型不斉Tsuji–Trost反応
  • Author(s): 北村雅人
  • Organizer: 第24回万有シンポジウム―有機合成化学の最前線―
  • Place of Presentation: 札幌
  • Invited
• [Book] e-EROS (2013)
  • Author(s): Masato Kitamura
  • Total Pages: 1
  • Publisher: Ferrocene, 1,1'-bis[(2R,4R)-2,4-diethyl-1-phosphetanyl]-, stereoisomer; Ferrocene, 1,1'-bis[(2S,4S)-2,4-diethyl-1-phosphetanyl]-, stereoisomer, RN01622
• [Book] Comprehensive Chirality (2012)
  • Author(s): Masaki Tsukamoto, Masato Kitamura
  • Total Pages: 4
  • Publisher: Reduction – Hydrogenation: C ═ C; Chemoselective.
• [Book] Comprehensive Chirality (2012)
  • Author(s): Seiji Suga, Masato Kitamura
  • Total Pages: 5
  • Publisher: Asymmetric 1,2-Addition of Organometallics to Carbonyl and Imine Groups.