Development of a novel method to generate nitrogen-centered radical species and its application to amination reactions

• Project/Area Number: 16K17868
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: Kiyokawa Kensuke 大阪大学, 工学研究科, 助教 (80632364)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 超原子価ヨウ素 / ヨウ素 / アミノ化 / ラジカル / 有機化学 / 合成化学

Outline of Final Research Achievements

In the presence of a metal catalyst, the amination of a C－H bond of aromatic compounds by a nitrogen-centered radical species generated from a hypervalent iodine reagent containing a phthalimidate proceeded to afford aniline derivatives albeit in low yield. In addition, an amination of enol silyl ether derived from various ketones proceeded effectively to provide α-aminated ketones in good yields. These results demonstrate a novel reactivity of hypervalent iodine reagents containing a phthalimidate.

Research Products

• [Journal Article] Oxidative Cyclization of β,γ-Unsaturated Carboxylic Acids Using Hypervalent Iodine Reagents: An Efficient Synthesis of 4-Substituted Furan-2-ones (2017)
  • Author(s): Kiyokawa Kensuke、Minakata Satoshi、Takemoto Kenta、Yahata Shunsuke、Kojima Takumi
  • Journal Title: Synthesis Volume: 49 Issue: 13 Pages: 2907-2912
  • DOI: 10.1055/s-0036-1588987
  • Peer Reviewed
• [Journal Article] Hypervalent Iodine(III)-Mediated Decarboxylative Ritter-Type Amination Leading to the Production of α-Tertiary Amine Derivatives (2017)
  • Author(s): Kiyokawa Kensuke、Watanabe Tomoki、Fra Laura、Kojima Takumi、Minakata Satoshi
  • Journal Title: The Journal of Organic Chemistry Volume: 82 Issue: 22 Pages: 11711-11720
  • DOI: 10.1021/acs.joc.7b01202
  • Peer Reviewed
• [Journal Article] Catalytic Activation of 1-Cyano-3,3-dimethyl-3-(1H)-1,2-benziodoxole with B(C6F5)3 Enabling the Electrophilic Cyanation of Silyl Enol Ethers (2017)
  • Author(s): Nagata Takaya、Matsubara Hiroki、Kiyokawa Kensuke、Minakata Satoshi
  • Journal Title: Organic Letters Volume: 19 Issue: 17 Pages: 4672-4675
  • DOI: 10.1021/acs.orglett.7b02313
  • Peer Reviewed
• [Journal Article] Recent Advances in the Synthesis of β-Ketonitriles (2017)
  • Author(s): Kiyokawa Kensuke、Minakata Satoshi、Nagata Takaya
  • Journal Title: Synthesis Volume: 50 Issue: 03 Pages: 485-498
  • DOI: 10.1055/s-0036-1589128
  • Peer Reviewed
• [Journal Article] Ritter-Type Amination of C-H Bonds at Tertiary Carbon Centers Using Iodic Acid as an Oxidant (2016)
  • Author(s): Kensuke Kiyokawa, Kenta Takemoto, and Satoshi Minakata
  • Journal Title: Chemical Communications Volume: 52 Issue: 89 Pages: 13082-13085
  • DOI: 10.1039/c6cc07164c
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Electrophilic Cyanation of Boron Enolates: Efficient Access to Various β-Ketonitrile Derivatives (2016)
  • Author(s): Kensuke Kiyokawa, Takaya Nagata, and Satoshi Minakata
  • Journal Title: Angewandte Chemie International Edition Volume: 55 Issue: 35 Pages: 10458-10462
  • DOI: 10.1002/anie.201605445
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 単体ヨウ素/超原子価ヨウ素系を活用したカルボン酸の脱炭酸酸素官能基化 (2018)
  • Author(s): 奥松大地，清川謙介，南方聖司
  • Organizer: 日本化学会第98春季年会
• [Presentation] ヨウ素酸化剤を活用する第三級C-H結合の酸素官能基化 (2018)
  • Author(s): 清川謙介，伊東 亮, 南方聖司
  • Organizer: 日本化学会第98春季年会
• [Presentation] 次亜ヨウ素酸tert-ブチルを活用したスルファマートエステルを窒素源とするオレフィン類のアジリジン化 (2018)
  • Author(s): 中村彰悟，清川謙介, 南方聖司
  • Organizer: 日本化学会第98春季年会
• [Presentation] 超原子価ヨウ素試剤を利用する脱炭酸リッター型アミノ化反応 (2017)
  • Author(s): 渡部友貴、清川謙介、南方聖司
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学 日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] Ritter-Type Amination of C-H Bonds at Tertiary Carbon Centers Using Iodic Acid as an Oxidant (2017)
  • Author(s): Kensuke Kiyokawa, Kenta Takemoto, Satoshi Minakata
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学 日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] 五酸化二ヨウ素を活用する第三級C-H結合の酸素官能化 (2017)
  • Author(s): 伊東 亮、竹本憲太、清川謙介、南方聖司
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学 日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] 次亜ヨウ素酸tert-ブチルを活用したスルファマートエステルの分子内C-Hアミノ化反応 (2017)
  • Author(s): 岩井田晃次、清川謙介、南方聖司
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学 日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] Electrophilic Cyanation of Boron Enolates (2017)
  • Author(s): Takaya Nagata, Kensuke Kiyokawa, Satoshi Minakata
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学 日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] N-ヒドロキシフタルイミド触媒を利用する第三級炭素のメタルフリー官能基化 (2017)
  • Author(s): 清川謙介, 伊東 亮, 竹本憲太, 南方聖司
  • Organizer: 第10回 有機触媒シンポジウム
• [Presentation] 超原子価ヨウ素/単体ヨウ素系を活用するカルボン酸の脱炭酸官能基化 (2017)
  • Author(s): 奥松大地, 清川謙介, 南方聖司
  • Organizer: 第7回CSJ化学フェスタ
• [Presentation] 五酸化二ヨウ素を酸化剤として活用する第三級C-H結合の酸素官能化 (2017)
  • Author(s): 伊東 亮, 清川謙介, 南方聖司
  • Organizer: 第20回ヨウ素学会シンポジウム
• [Presentation] 次亜ヨウ素酸tert-ブチルを活用したスルファマートエステルの分子内C-Hアミノ化 (2017)
  • Author(s): 岩井田晃次, 清川謙介, 南方聖司
  • Organizer: 第37回有機合成若手セミナー「明日の有機合成を担う人のために」
• [Presentation] ヨウ素酸化剤を活用する第三級C-H結合酸素官能化反応 (2017)
  • Author(s): 伊東 亮, 清川謙介, 南方聖司
  • Organizer: 第6回 JACI/GSCシンポジウム
• [Presentation] ヨウ素酸を酸化剤として用いる第三級C-H結合のリッター型アミノ化 (2016)
  • Author(s): 竹本憲太、清川謙介、南方聖司
  • Organizer: 第43回有機典型元素化学討論会
  • Place of Presentation: 仙台市民会館
  • Year and Date: 2016-12-08
• [Presentation] ホウ素エノラートの求電子的シアノ化反応を利用した高効率β-ケトニトリル合成 (2016)
  • Author(s): 永田貴也、清川謙介、南方聖司
  • Organizer: 第6回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2016-11-14
• [Presentation] ヨウ素酸化剤を活用する第三級炭素のC-H結合酸素官能化 (2016)
  • Author(s): 伊東 亮、清川謙介、南方聖司
  • Organizer: 第6回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2016-11-14
• [Presentation] Decarboxylative Ritter-Type Amination Using Iodine Reagents (2016)
  • Author(s): Laura Fra Fernandez, Tomoki Watanabe, Kilian Muniz, Kensuke Kiyokawa, Youhei Takeda, Satoshi Minakata
  • Organizer: International Symposium on C-O Activation (ISCO-2016)
  • Place of Presentation: 姫路商工会議所
  • Year and Date: 2016-10-25
  • Int'l Joint Research
• [Presentation] Electrophilic Cyanation of Boron Enolates: Efficient Access to β-Ketonitriles (2016)
  • Author(s): Takaya Nagata, Kensuke Kiyokawa, Satoshi Minakata
  • Organizer: 20th International Symposium on Homogeneous Catalysis (ISHCXX)
  • Place of Presentation: 京都テルサ
  • Year and Date: 2016-07-10
  • Int'l Joint Research
• [Presentation] Ritter-Type Amination of C-H Bonds at Tertiary Carbon Centers Using Iodic Acid as an Oxidant (2016)
  • Author(s): Kensuke Kiyokawa, Kenta Takemoto, Satoshi Minakata
  • Organizer: 5th International Conference on Hypervalent Iodine Chemistry (ICHIC2016)
  • Place of Presentation: Eurotel Victoria
  • Year and Date: 2016-07-03
  • Int'l Joint Research
• [Presentation] ヨウ素反応剤を用いた脱炭酸リッター型アミノ化反応 (2016)
  • Author(s): 渡部友貴、清川謙介、南方聖司
  • Organizer: 第19回ヨウ素学会シンポジウム
  • Place of Presentation: 千葉大学