Development of nucleophilic cyanation to non-activated alkynes

• Project/Area Number: 21590003
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Chiba University
• Principal Investigator: ARAI Shigeru 千葉大学, 大学院・薬学研究院, 准教授 (20285224)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2011: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2010: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2009: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: アルキン / シアノ化 / パラジウム / 触媒 / 触媒的シアノ化 / シアノパラデーション / 酸素

Research Abstract

Nucleophilic cyanation has been developed by using catalytic amount of Pd(II) with non-activated alkynes and CN source. This fundamental and non-reported transformation in organometallic chemistry is named as cyanopalladation which promote electrophilic activation of alkynes and smooth nucleophilic attack from external CN source such as TMSCN. Furthermore, enynes and dienynes which have conjugated enyne units have been found for quite suitable substrates to install CN functionality in regio- and stereoselective fashion through cyclization protocol.

Research Products

• [Journal Article] Catalytic Dicyanative [4+2]Cycloaddition Triggered byCyanopalladation Using Ene-enynesand Cyclic Enynes with MethylAcrylate (2010)
  • Author(s): Arai, S, , Koike, Y., Hada, H., Nishida, A
  • Journal Title: J. Org. Chem Volume: 75 Pages: 7573-7579
  • Peer Reviewed
• [Journal Article] Catalytic Dicyanative [4+2]Cycloaddition Triggered byCyanopalladation of ConjugatedEnynes Under Aerobic Conditions (2010)
  • Author(s): Arai, S, , Koike, Y., Hada, H, Nishida, A.
  • Journal Title: J. Am. Chem. Soc Volume: 132
  • Peer Reviewed
• [Journal Article] Catalytic Dicyanative 5-exo- and6-endo-Cyclization Triggered by Cyanopalladation of Alkynes (2010)
  • Author(s): Arai, S, , Koike, Y., Nishida, A
  • Journal Title: Adv. Synth. Catal Volume: 352 Pages: 893-900
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Cyanation of Carbon-Carbon Triple Bonds under Aerobic Conditions (2010)
  • Author(s): Arai S., Sato T., Koike Y., Hayashi M., Nishida A
  • Journal Title: Angew. Chem. Int. Ed, Highlighted in Synth. Org. Chem. Jpn Volume: 48,68
  • Peer Reviewed
• [Journal Article] Catalytic Dicyanative [4+2] Cycloaddition Triggered by Cyanopalladation Using Ene-Enynes and Cyclic Enynes with Methyl Acrylate (2010)
  • Author(s): Arai, S, ; Koike, Y. ; Hada, H ; Nishida, A.
  • Journal Title: Journal of Organic Chemistry Volume: 75 Pages: 7573-7579
  • Peer Reviewed
• [Journal Article] Catalytic Dicyanative [4+2] Cycloaddition Triggered by Cyanopalladation of Conjugated Enynes Under Aerobic Conditions (2010)
  • Author(s): Arai, S, ; Koike, Y.; Hada, H ; Nishida, A.
  • Journal Title: Journal of American Chemical Society 132 Pages: 4523-4524
  • Peer Reviewed
• [Journal Article] Catalytic Dicyanative 5-exo-and 6-endo-Cyclization Triggered by Cyanop alladation of Alkynes (2010)
  • Author(s): Arai, S, ; Koike, Y.; Nishida, A.
  • Journal Title: Advanced Synthesis and Catalysis 351 Pages: 893-900
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of Hydroisoquinoline Derivatives, a Key Intermediate for Manzamine Synthesis, by Diels-Alder Reaction Using 4-Amino-2-siloxybutadiene (2009)
  • Author(s): Mihara Y., Matsumura T., Terauchi Y., Akiba M., Arai S., Nishida, A
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 82 Pages: 1520-1527
  • NAID: 10027170873
  • Peer Reviewed
• [Journal Article] Catalytic 1,2-Dicyanation of Alkynes by Palladium(II) under Aerobic Conditions (2009)
  • Author(s): Arai S, Sato T., Nishida A
  • Journal Title: Adv. Synth. Catal Volume: 351,11
  • Peer Reviewed
• [Journal Article] Catalytic 1, 2-Dicyanation of Alkynes by Palladium (II) under Aerobic Conditions (2009)
  • Author(s): Arai, S, ; Sato, T.; Nishida, A.
  • Journal Title: Advanced Synthesis and Catalysis 350 Pages: 1897-1904
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Cyanation of Carbon-Carbon Triple Bonds Under Aerobic Conditions (2009)
  • Author(s): Arai, S, ; Sato, T.; Koike, Y.; Hayashi, M.; Nishida, A.
  • Journal Title: Angewandte Chemie International Edition 48 Pages: 4528-4531
  • Peer Reviewed
• [Presentation] パラジウム触媒を用いるアルキンのシアノ化 (2011)
  • Author(s): 荒井秀, 小池由佳, 五十嵐知宏, 楊暁菲, 西田篤司
  • Organizer: 第37回反応と合成の進歩シンポジウム講演要旨集
  • Place of Presentation: 徳島
  • Year and Date: 2011-11-07
• [Presentation] パラジウム触媒を用いるアルキンのシアノ化 (2011)
  • Author(s): 荒井秀
  • Organizer: 第37回反応と合成の進歩シンポジウム
  • Place of Presentation: あわぎんホール(徳島)
  • Year and Date: 2011-11-07
• [Presentation] シクロプロパン融合型院疎林骨格を有するLundurine類の合成研究 (2011)
  • Author(s): 星真幸, 金子統, 荒井秀, 西田篤司
  • Organizer: 第41回複素環化学討論会講演要旨集
  • Place of Presentation: 崇城大学市民ホール
  • Year and Date: 2011-10-22
• [Presentation] 炭素-炭素多重結合への触媒的シアノ化を基軸とする環化反応 (2011)
  • Author(s): 天児由佳, 荒井秀, 西田篤司
  • Organizer: 第55回日本薬学会関東支部大会講演要旨集
  • Place of Presentation: 東邦大学
  • Year and Date: 2011-10-08
• [Presentation] 炭素-炭素多重結合への触媒的シアノ化を基軸とする環化反応 (2011)
  • Author(s): 天児由佳
  • Organizer: 第55回日本薬学会関東支部大会
  • Place of Presentation: 東邦大学(千葉)
  • Year and Date: 2011-10-08
• [Presentation] Pd-Catalyzed Cyanation of Non-activated Alkynes (2011)
  • Author(s): Shigeru Arai, Yuka Koike, Tomohiro Igarashi, Xiaofei Yang, Atsushi Nishida
  • Organizer: 58th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Nagoya
  • Year and Date: 2011-09-08
• [Presentation] Pd-Catalyzed Cyanation of Non-activated Alkynes (2011)
  • Author(s): 荒井秀
  • Organizer: 58th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: 名古屋大学
  • Year and Date: 2011-09-08
• [Presentation] アルキンの触媒的シアノ化と環化反応への応用 (2010)
  • Author(s): 小池由佳, 羽田博彦, 荒井秀, 西田篤司
  • Organizer: 日本薬学会第130年会講演プログラム
  • Place of Presentation: 岡山
  • Year and Date: 2010-03-30
• [Presentation] アルキンの触媒的シアノ化と環化反応への応用 (2010)
  • Author(s): 小池由佳、羽由博彦、荒井秀、西田篤司
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山市
  • Year and Date: 2010-03-28
• [Presentation] Palladium catalyzed cyanation of alkynes and its application (2010)
  • Author(s): Shigeru Arai, Yuka Koike, Atsushi Nishida
  • Organizer: American Chemical Society 239^<th> National Meeting
  • Place of Presentation: サンフランシスコ(米国)
  • Year and Date: 2010-03-25
• [Presentation] Palladium catalyzed cyanation of alkynes and its application (2010)
  • Author(s): Shigeru Arai, Yuka Koike, Atsushi Nishida
  • Organizer: American Chemical Society 239^<th>National Meeting
  • Place of Presentation: San Francisco, CA
  • Year and Date: 2010-03-23
• [Presentation] パラジウム触媒.酸素系におけるシアノ基導入型環化反応 (2009)
  • Author(s): 小池由佳, 羽田博彦, 荒井秀, 西田篤司
  • Organizer: 第39回複素環化学討論会講演要旨集
  • Place of Presentation: 柏
  • Year and Date: 2009-10-15
• [Presentation] パテジウム触媒-酸素系におけるシアノ基導入型環化反応 (2009)
  • Author(s): 小池由佳、羽由博彦、荒井秀、西田篤司
  • Organizer: 第39回複素環化学討論会
  • Place of Presentation: 千葉県柏市
  • Year and Date: 2009-10-14
• [Presentation] パラジウム触媒.酸素系におけるエンイン化合物のシアノ基導入型環化反応 (2009)
  • Author(s): 小池由佳, 佐藤崇, 林迪乃, 荒井秀, 西田篤司
  • Organizer: 第25回有機合成化学セミナー講演要旨集
  • Place of Presentation: 阿蘇
  • Year and Date: 2009-09-09
• [Presentation] パラジウム触媒によるアルキンのシアノ化と環化反応への応用 (2009)
  • Author(s): 荒井秀, 小池由佳, 西田篤司
  • Organizer: 第3回日本化学会関東支部大会講演要旨集
  • Place of Presentation: 早稲田
  • Year and Date: 2009-09-04
• [Presentation] パテジウム触媒によるアルキンのシアノ化と環化反応への応用 (2009)
  • Author(s): 荒井秀、小池由佳、西田篤司
  • Organizer: 第3回日本化学会関東支部大会
  • Place of Presentation: 早稲田大学
  • Year and Date: 2009-09-04
• [Presentation] パラジウム触媒-酸素系におけるエンイン化合物のシアノ基導入型環化反応 (2009)
  • Author(s): 小池由佳、佐藤崇、林迪乃、荒井秀、西田篤司
  • Organizer: 第25回有機合成化学セミナー
  • Place of Presentation: 阿蘇
  • Year and Date: 2009-05-28
• [Book] 触媒的二重シアノ環化反応,ワンポットジアゾアルドール反応,使える!有機合成反応241実践ガイド (2010)
  • Author(s): 西田篤司, 荒井秀, 西田篤司, 荒井秀, 丸岡啓二, 他
• [Book] 使える! 有機合成反応241実践ガイド 丸岡啓二他編集 (2010)
  • Author(s): 荒井秀、西田篤司
  • Total Pages: 4
  • Publisher: 化学同人