Organic Synthesis Using Various Valences of Iodine Reagents

• Project/Area Number: 25288047
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: Minakata Satoshi 大阪大学, 工学(系)研究科(研究院), 教授 (90273599)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2015: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2014: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2013: ¥10,660,000 (Direct Cost: ¥8,200,000、Indirect Cost: ¥2,460,000)
• Keywords: ヨウ素 / 超原子価ヨウ素 / 触媒反応 / アミノ化 / アミノ化反応 / 脱炭酸 / 酸化反応 / ハロゲン結合 / 不斉合成

Outline of Final Research Achievements

This research project was carried out for the development of novel iodine reagents, especially iodine(I), (III), and (V) compounds, and their use in organic synthesis. The synthesis of iodine(I) reagents, which has an unique Lewis acidity, and its application to organic reactions were achieved. In addition, novel iodine(III) reagents containing nitrogen functional groups as a ligand were successfully synthesized, and they could be applied to amination reactions. The new type of amination reaction using iodine(V) reagents was also developed.

Research Products

• [Journal Article] Synthesis and Structure of Hypervalent Iodine(III) Reagents Containing Phthalimidate and Application to Oxidative Amination Reactions (2015)
  • Author(s): Kensuke Kiyokawa, Tomoki Kosaka, Takumi Kojima, and Satoshi Minakata
  • Journal Title: Angew. Chem., Int. Ed. Volume: 54 Issue: 46 Pages: 13719-13723
  • DOI: 10.1002/anie.201506805
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides (2015)
  • Author(s): Kensuke Kiyokawa, Takumi Kojima, Yusuke Hishikawa, and Satoshi Minakata
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 44 Pages: 15548-15552
  • DOI: 10.1002/chem.201503298
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A facile synthesis of functionalized 7,8-diaza[5]helicenes through an oxidative ring-closure of 1,1’-binaphthalene-2,2’-diamines (BINAMs) (2015)
  • Author(s): Youhei Takeda, Masato Okazaki, Yoshiaki Maruoka, and Satoshi Minakata
  • Journal Title: Beilstein J. Org. Chem. Volume: 11 Pages: 9-15
  • DOI: 10.3762/bjoc.11.2
  • Peer Reviewed
• [Journal Article] 2-Halogenoimidazolium Salt Catalyzed Aza-Diels-Alder Reaction through Halogen-Bond Formation (2015)
  • Author(s): Youhei Takeda, Daichi Hisakuni, Chun-Hsuan Lin, and Satoshi Minakata
  • Journal Title: Org. Lett. Volume: 17 Issue: 2 Pages: 318-321
  • DOI: 10.1021/ol503426f
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Revisiting Phosphorus Analogues of Phthalimides and Naphthalimides: Syntheses and Comparative Studies (2015)
  • Author(s): Youhei Takeda, Takuya Nishida, Kota Hatanaka, and Satoshi Minakata
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 4 Pages: 1666-1672
  • DOI: 10.1002/chem.201405494
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Straightforward Synthesis of 1,2-Dicyanoalkanes from Nitroalkenes and Silyl Cyanide Mediated by Tetrabutylammonium Fluoride (2015)
  • Author(s): Kensuke Kiyokawa, Takaya Nagata, Junpei Hayakawa, and Satoshi Minakata
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 3 Pages: 1280-1285
  • DOI: 10.1002/chem.201404780
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hypervalent Iodine(III)-Mediated Oxidative Decarboxylation of β,γ-Unsaturated Carboxylic Acids (2014)
  • Author(s): Kensuke Kiyokawa, Shunsuke Yahata, Takumi Kojima, and Satoshi Minakata
  • Journal Title: Org. Lett. Volume: 16 Issue: 17 Pages: 4646-4649
  • DOI: 10.1021/ol5022433
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Oxidative Skeletal Rearrangement of 1,1’-Binaphthalene-2,2’-Diamines (BINAMs) via C-C Bond Cleavage and Nitrogen Migration: A Versatile Synthesis of U-Shaped Azaacenes (2014)
  • Author(s): Youhei Takeda, Masato Okazaki, and Satoshi Minakata
  • Journal Title: Chem. Commun. Volume: 50 Issue: 71 Pages: 10291-10294
  • DOI: 10.1039/c4cc04911j
  • Peer Reviewed
• [Journal Article] 2,6-Diphospha-s-indacene-1,3,5,7(2H,6H)-tetraone: A Phosphorus Analogue of Aromatic Diimides with the Minimal Core Exhibiting High Electron-accepting Ability (2014)
  • Author(s): Youhei Takeda, Takuya Nishida, and Satoshi Minakata
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 33 Pages: 10266-10270
  • DOI: 10.1002/chem.201403735
  • Peer Reviewed
• [Journal Article] Pd/NHC-Catalyzed Enantiospecific and Regioselective Suzuki-Miyaura Arylation of 2-Arylaziridines: Synthesis of Enantioenriched 2-Arylphenethylamine Derivatives (2014)
  • Author(s): Youhei Takeda, Yuki Ikeda, Akinobu Kuroda, Shino Tanaka, and Satoshi Minakata
  • Journal Title: J. Am. Chem. Soc. Volume: 136 Issue: 24 Pages: 8544-8547
  • DOI: 10.1021/ja5039616
  • Peer Reviewed
• [Journal Article] Oxidative Dimerization of (Hetero)aromatic Amines Utilizing t‐BuOI Leading to (Hetero)aromatic Azo Compounds: Scope and Mechanistic Studies (2013)
  • Author(s): Satoshi Minakata
  • Journal Title: J. Org. Chem. Volume: 78 Issue: 23 Pages: 12090-12105
  • DOI: 10.1021/jo402120w
  • Peer Reviewed
• [Journal Article] Metal-Free Aziridination of Styrene Derivatives with Iminoiodinane Catalyzed by a Combination of Iodine and Ammonium Iodide (2013)
  • Author(s): Satoshi Minakata
  • Journal Title: Org. Lett. Volume: 15 Issue: 18 Pages: 4858-4861
  • DOI: 10.1021/ol402276f
  • Peer Reviewed
• [Journal Article] PCy_3-Catalyzed Ring-Expansion of Aziridinofullerenes with CO_2 and Aryl Isocyanates : Evidence for a Two-Conseutive Nucleophilic Substitution Pathway on the Fullerene Cage (2013)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem. Eur. J. Volume: 19 Issue: 40 Pages: 13479-13483
  • DOI: 10.1002/chem.201301617
  • Peer Reviewed
• [Journal Article] Hypervalent Iodine(III)-Induced Oxidative [4+2] Annulation of o-Phenylenediamines and Electron-Deficient Alkynes : Direct Synthesis of Quinoxalines from Alkyne Substrates under Metal-Free Conditions (2013)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem. Commun. Volume: 49 Issue: 81 Pages: 9266-9268
  • DOI: 10.1039/c3cc45469j
  • Peer Reviewed
• [Journal Article] A Practical Synthesis of Azobenzenes through Oxidative Dimerization of Aromatic Amines Using tert-Butyl Hypoiodite (2013)
  • Author(s): Satoshi Minakata
  • Journal Title: Synthesis Volume: 45 Issue: 08 Pages: 1029-1033
  • DOI: 10.1055/s-0032-1318388
  • Peer Reviewed
• [Presentation] ヨウ素触媒存在下、クロラミン-Nsを窒素源とするオレフィン類のビシナルジアミノ化 (2016)
  • Author(s): 平山 新，三輪勇人，南方聖司
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学、京田辺キャンパス
  • Year and Date: 2016-03-24
• [Presentation] ヨウ素酸とN-ヒドロキシフタルイミドを活用した第三級炭素のリッター型C-Hアミノ化 (2016)
  • Author(s): 竹本憲太，伊東 亮，清川謙介，南方聖司
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学、京田辺キャンパス
  • Year and Date: 2016-03-24
• [Presentation] Iodine-catalyzed diamination of olefins using haloamide salt (2015)
  • Author(s): Satoshi Minakata, Arata Hirayama, Shino Tanaka
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu, Hawaii
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Synthesis and structure of hypervalent iodine(III) reagent containing phthalimidate and its application to oxidative amination reaction (2015)
  • Author(s): Kensuke Kiyokawa, Tomoki Kosaka, Satoshi Minakata
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu, Hawaii
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Hypervalent iodine(III)-mediated decarboxylative functionalization of β,γ-unsaturated carboxylic acids (2015)
  • Author(s): Takumi Kojima, Kensuke Kiyokawa, Satoshi Minakata
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu, Hawaii
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Ritter-type C–H amination using N-hydroxyphthalimide and iodic acid (2015)
  • Author(s): Kenta Takemoto, Kensuke Kiyokawa, Satoshi Minakata
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu, Hawaii
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] ヨウ素酸とN-ヒドロキシフタルイミドを用いた第三級C-H結合のリッター型アミノ化 (2015)
  • Author(s): 竹本憲太, 清川謙介, 南方聖司
  • Organizer: 第18回ヨウ素学会シンポジウム
  • Place of Presentation: 千葉大学、千葉県千葉市
  • Year and Date: 2015-09-16
• [Presentation] ヨウ素触媒を用いたクロラミン塩を窒素源とするβ,γ-不飽和カルボン酸の脱炭酸アミノ化反応 (2015)
  • Author(s): 小嶋匠実・菱川友輔・清川謙介・ 南方聖司
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス 千葉
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] フタルイミデートを有する超原子価ヨウ素試薬の合成とイミド化反応への活用 (2015)
  • Author(s): 小坂知輝・清川謙介・南方聖司
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス 千葉
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 超原子価ヨウ素試薬を活用するβ,γ-不飽和カルボン酸の脱炭酸酸素官能化 (2014)
  • Author(s): 矢羽田駿介，清川謙介， 南方聖司
  • Organizer: 第41回有機典型元素化学討論会
  • Place of Presentation: 宇部市文化会館文化ホール 宇部
  • Year and Date: 2014-11-27 – 2014-11-29
• [Presentation] 超原子価ヨウ素試薬を用いるβ,γ-不飽和カルボン酸の脱炭酸イミド化反応 (2014)
  • Author(s): 小嶋匠実，清川謙介，南方聖司
  • Organizer: 第4回CSJ化学フェスタ2014
  • Place of Presentation: タワーホール船堀 東京
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] 超原子価ヨウ素試薬を用いるβ,γ-不飽和カルボン酸の脱炭酸イミド化反応 (2014)
  • Author(s): 小嶋匠実，清川謙介，南方聖司
  • Organizer: 第17回ヨウ素学会シンポジウム
  • Place of Presentation: 千葉大学けやき会館 千葉
  • Year and Date: 2014-09-19
• [Presentation] Hypervalent Iodine(III)-Mediated Oxidative Decarbonylation of β,γ-Unsaturated Carboxylic Acids (2014)
  • Author(s): Kensuke Kiyokawa，Shunsuke Yahata，Takumi Kojima, Satoshi Minakata
  • Organizer: 4th International Conference on Hypervalent Iodine Chemistry
  • Place of Presentation: Hilton Narita, Chiba
  • Year and Date: 2014-07-02 – 2014-07-05
• [Presentation] 超原子価ヨウ素試剤を用いるアリルカルボン酸の脱炭酸アセトキシ化反 (2014)
  • Author(s): 南方聖司
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学
  • Invited
• [Presentation] ヨウ素／アンモニウム塩触媒を活用したイミノヨージナンを窒素源とするアジリジン合成 (2013)
  • Author(s): 南方聖司
  • Organizer: ヨウ素学会
  • Place of Presentation: 千葉大学
  • Invited
• [Presentation] ヨードベンゼンジアセタートを活用するo-フェニレンジアミンと電子不足アルキンからのキノキサリン誘導体の合 (2013)
  • Author(s): 南方聖司
  • Organizer: 第３回CSJ化学フェスタ
  • Place of Presentation: 船堀タワーホール（東京）
  • Invited