Direct C-N Bond Formation Using I-N Bonding Hypervalent Iodine

• Project/Area Number: 15K17819
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Chiba University
• Principal Investigator: Moriyama Katsuhiko 千葉大学, 大学院理学研究院, 准教授 (00509044)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: アミノ化反応 / 複素環化合物 / 超原子価ヨウ素 / ハロゲン化 / ヨウ素 / アミノ化 / インドール / 超原子価化合物

Outline of Final Research Achievements

We have developed the design of I-N bonding hypervalent iodine compounds and the direct amination of heterocycles using these compounds as low environmental load type transformation in this work. As a result, Csp2-Csp2 bromoamination, remote Csp2-Csp3 iodoamination, and catalytic 3-amination of indole derivatives were accomplished by handling I-N bonding hypervalent iodine compounds. Furthermore, synthesis of various amino-substituted indole derivatives from products of these transformations were succeeded.

Research Products

• [Journal Article] One-pot preparation of 4-aryl-3-bromocoumarins from 4-aryl-2-propynoic acids with diaryliodonium salts, TBAB, and Na2S2O8 (2018)
  • Author(s): Sasaki Teppei、Moriyama Katsuhiko、Togo Hideo
  • Journal Title: Beilstein Journal of Organic Chemistry Volume: 14 Pages: 345-353
  • DOI: 10.3762/bjoc.14.22
  • Peer Reviewed / Open Access
• [Journal Article] 1,3-Iodo-amination of 2-methyl indoles via Csp2-Csp3 dual functionalization with iodine reagent (2018)
  • Author(s): Katsuhiko Moriyama, Tsukasa Hamada, Kazuma Ishida, Hideo Togo
  • Journal Title: Chemical Communications Volume: 54 Issue: 34 Pages: 4258-4261
  • DOI: 10.1039/c8cc00352a
  • Peer Reviewed
• [Journal Article] Introduction of Quinolines and Isoquinolines onto Nonactivated α-C?H Bond of Tertiary Amides through a Radical Pathway (2017)
  • Author(s): Okugawa Naoki、Moriyama Katsuhiko、Togo Hideo
  • Journal Title: The Journal of Organic Chemistry Volume: 82 Issue: 1 Pages: 170-178
  • DOI: 10.1021/acs.joc.6b02303
  • Peer Reviewed / Open Access
• [Journal Article] Catalytic dehydrogenateive dual functionalization of ethers: dealkylation-oxidation-bromination accompanyied by C-O bond cleavage via aerobic ocidation of bromide (2017)
  • Author(s): Katsuhiko Moriyama, Tsukasa Hamada, Yu Nakamura, Hideo Togo
  • Journal Title: Chemical Communications Volume: 53 Issue: 49 Pages: 6565-6568
  • DOI: 10.1039/c7cc02166f
  • Peer Reviewed
• [Journal Article] Preparation of 3-Iodoquinolines from N-Tosyl-2-propynylamines with Diaryliodonium Triflate and N-Iodosuccinimide (2017)
  • Author(s): Sasaki Teppei、Moriyama Katsuhiko、Togo Hideo
  • Journal Title: The Journal of Organic Chemistry Volume: 82 Issue: 22 Pages: 11727-11734
  • DOI: 10.1021/acs.joc.7b01433
  • Peer Reviewed / Open Access
• [Journal Article] Recent Advances in Oxidative C-C Coupling Reaction of Amides with Carbon Nucleophiles (2017)
  • Author(s): Katsuhuko Moriyama
  • Journal Title: Tetrahedron Letters Volume: 58 Pages: 4655-4662
  • Peer Reviewed
• [Journal Article] One-pot transformation of Aliphatic Carboxylic Acids into N-Alkylsuccinimides with NIS and NCS/NaI (2016)
  • Author(s): Yuhta Nakai, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: European Journal of Organic Chemistry Volume: 19 Issue: 4 Pages: 768-772
  • DOI: 10.1002/ejoc.201501315
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Direct Transformation of Ethylarenes into Primary Aromatic Amides with N‐Bromosuccinimide and I2-Aqueous NH3 (2016)
  • Author(s): Shohei Shimokawa, Yuhsuke Kawagoe, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: Organic Letters Volume: 18 Issue: 4 Pages: 784-787
  • DOI: 10.1021/acs.orglett.6b00048
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Direct Preparation of 3-Iodochromenes from 3-Aryl- and 3-Alkyl-2-propyn-1-ols with Diaryliodonium Salts and NIS (2016)
  • Author(s): Teppei Sasaki, Kotaro Miyagi, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: Organic Letters Volume: 18 Issue: 5 Pages: 944-947
  • DOI: 10.1021/acs.orglett.5b03651
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Preparation of 5-Aryl-2-Alkyltetrazoles with Aromatic Aldehydes, Alkylhydrazine, Di-t-butyl Azodicarboxylate, and [bis(trifluoroacetoxy)iodo]benzene (2016)
  • Author(s): Tarou Imai, Ryo Harigae, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: The Journal of Organic Chemistry Volume: 81 Issue: 9 Pages: 3975-3980
  • DOI: 10.1021/acs.joc.6b00606
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Magnesium Lewis Acid Assisted Oxidative Bromoetherification Involving Bromine Transfer from Alkyl Bromides with Aldehydes by Umpolung of Bromide (2016)
  • Author(s): Katsuhiko Moriyama, Chihiro Nishinohara, Hideo Togo
  • Journal Title: Chemistry - A European Journal Volume: 22 Issue: 34 Pages: 11934-11939
  • DOI: 10.1002/chem.201602055
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nitroxyl-Radical-Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N-Halogenation (2016)
  • Author(s): K. Moriyama, M. Kuramochi, K. Fujii, T. Morita, H. Togo
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 47 Pages: 14546-14551
  • DOI: 10.1002/anie.201607223
  • Peer Reviewed
• [Journal Article] Preparation of Heterocyclic(aryl)iodonium Imides as Imide Combined Hypervalent Iodines Containing Heterocycles (2016)
  • Author(s): K. Ishida, H. Togo, K. Moriyama
  • Journal Title: Chemistry - An Asian Journal Volume: 11 Issue: 24 Pages: 3583-3588
  • DOI: 10.1002/asia.201601349
  • Peer Reviewed / Open Access
• [Journal Article] Regioselective Csp2-H dual functionalization of indoles using hypervalent iodine(III): bromo-amination via 1,3-migration of imides on indolyl(phenyl)iodonium imides (2015)
  • Author(s): Katsuhiko Moriyama, Kazuma Ishida, Hideo Togo
  • Journal Title: Chemical Communication Volume: 51 Issue: 12 Pages: 2273-2276
  • DOI: 10.1039/c4cc09077b
  • Peer Reviewed
• [Journal Article] Facile One-Pot Transformation of Arenes into Aromatic Nitriles under Metal-Cyanide-Free Conditions (2015)
  • Author(s): Toshiyuki Tamura, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: European Journal of Organic Chemistry Volume: 2015 Issue: 9 Pages: 2023-2029
  • DOI: 10.1002/ejoc.201403672
  • Peer Reviewed
• [Journal Article] A One-Pot, Transition-Metal-Free Procedure for C-O, C-S, and C-N Bond Formation at the Benzylic Position of Methylarenes (2015)
  • Author(s): Hiroyuki Shimojo, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: Synthesis Volume: 47 Issue: 09 Pages: 1280-1290
  • DOI: 10.1055/s-0034-1380069
  • Peer Reviewed
• [Journal Article] 2,6-Bis(amido)benzoic acid with internal hydrogen bond as Bronsted acid catalyst for Friedel-Crafts reaction of indoles (2015)
  • Author(s): Katsuhiko Moriyama, Toru Sugiue, Yuki Saito, Shoichi Katsuta, and Hideo Togo
  • Journal Title: Advanced Synthesis & Catalysis Volume: 357 Issue: 9 Pages: 2143-2149
  • DOI: 10.1002/adsc.201401189
  • Peer Reviewed
• [Journal Article] One-pot preparation of 2,5-disubstituted and 2,4,5-trisubstituted oxazoles from aromatic ketones with molecular iodine, oxone, and trifluoromethanesulfonic acid in nitriles (2015)
  • Author(s): Sho Imai, Hiroki Kikui, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: Tetrahedron Volume: 71 Issue: 33 Pages: 5267-5274
  • DOI: 10.1016/j.tet.2015.06.022
  • Peer Reviewed
• [Journal Article] Introduction of Ether Groups onto Electron-Deficient Nitrogen-Containing Heteroaromatics Using Radical Chemistry under Transition-Metal-Free Conditions (2015)
  • Author(s): Naoki Okugawa, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: European Journal of Organic Chemistry Volume: 2015 Issue: 22 Pages: 4973-4981
  • DOI: 10.1002/ejoc.201500584
  • Peer Reviewed
• [Journal Article] Divergent Synthesis of α,γ-Disubstituted γ-Butyrolactones through Diastereoselective Bromo-lactonization Using Alkali Metal Bromides (2015)
  • Author(s): Katsuhiko Moriyama, Toru Sugiue, Chihiro Nishinohara, Hideo Togo
  • Journal Title: The Journal of Organic Chemistry Volume: 80 Issue: 18 Pages: 4973-4981
  • DOI: 10.1021/acs.joc.5b01497
  • Peer Reviewed
• [Journal Article] Oxidative Oxygen-Nucleophilic Bromo-Cyclization of Alkenyl Carbonyl Compounds Without Organic Wastes Using Alkali Metal Reagents in Green Solvent (2015)
  • Author(s): Katsuhiko Moriyama, Chihiro Nishinohara, Toru Sugiue, Hideo Togo
  • Journal Title: RSC Advances Volume: 5 Issue: 104 Pages: 85872-85878
  • DOI: 10.1039/c5ra19851h
  • Peer Reviewed
• [Journal Article] Transformation of N,N-diisopropylarylmethylamines into N-isopropylarylmethylamines with molecular iodine (2015)
  • Author(s): Masatoshi Ezawa, Katsuhiko Moriyama, Hideo Togo
  • Journal Title: Tetrahedron Letters Volume: 56 Issue: 48 Pages: 6689-6692
  • DOI: 10.1016/j.tetlet.2015.10.044
  • Peer Reviewed
• [Presentation] Amino-halogenation of Indoles as Dual Functionalization Using N-I Bonding Hypervalent Iodine Compounds (2018)
  • Author(s): Katsuhiko Moriyama
  • Organizer: International Congress on Pure & Applied Chemistry (ICPAC) 2018
  • Int'l Joint Research / Invited
• [Presentation] 銅触媒を用いたインドリル（アリール）ヨードニウムイミドの転位型炭素ー窒素結合形成反応 (2018)
  • Author(s): 渡辺 和寛、森山 克彦
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] ヨウ素試薬を用いた2-メチルインドール誘導体の遠隔ヨードアミノ化反応 (2018)
  • Author(s): 浜田 司、石田 一馬、東郷 秀雄、森山 克彦
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] 臭化物イオンの酸素酸化によるアルケニルアルコールの触媒的ブロモエーテル化反応 (2018)
  • Author(s): 冨塚 亮彦、浜田 司、森山 克彦
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] ニトロキシル触媒を用いたハロゲン化剤活性化によるアルケンのブロモエステル化反応 (2017)
  • Author(s): 倉持 昌子、森山 克彦
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶応義塾大学(神奈川県、横浜市)
  • Year and Date: 2017-03-16
• [Presentation] マグネシウムルイス酸の活性化による臭素移動型酸化的ブロモエーテル化反応 (2017)
  • Author(s): 森山 克彦、西ノ原 千尋、東郷 秀雄
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶応義塾大学(神奈川県、横浜市)
  • Year and Date: 2017-03-16
• [Presentation] 臭化物イオンの酸化を利用した環状エーテルの酸素官能基化反応 (2017)
  • Author(s): 浜田 司、東郷 秀雄、森山 克彦
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶応義塾大学(神奈川県、横浜市)
  • Year and Date: 2017-03-16
• [Presentation] Dual-Functionalization of Ethers via Aerobic Oxidation of Bromide Ion (2017)
  • Author(s): Tsukasa Hamada, Hideo Togo, Katsuhiko Moriyama
  • Organizer: The 8th International Meeting on Halogen Chemistry
  • Int'l Joint Research
• [Presentation] Dual Functionalization of Indoles via Amino-halogenation Using N-I Bonding Hypervalent Iodine Compounds (2017)
  • Author(s): Katsuhiko Moriyama
  • Organizer: The 8th International Meeting on Halogen Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Nitroxyl-Radical-Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N-Halogenation (2016)
  • Author(s): Masako Kuramochi, Hideo Togo, Katsuhiko Moriyama
  • Organizer: 2nd Joint Workshop on Chirality in Chiba University (WCCU) and Soft Molecule Activation (SMA)
  • Place of Presentation: Chiba University (Chiba)
• [Presentation] Regioselective C-H dual functionalization of indoles using hypervalent iodine(III) (2015)
  • Author(s): Katsuhiko Moriyama, Hideo Togo
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu（USA）
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] ハロゲン化合物を利用した酸化的二重官能基化反応の開発 (2015)
  • Author(s): 森山克彦
  • Organizer: 有機合成化学協会東海支部 総合講演会
  • Place of Presentation: 名古屋大学ベンチャービジネスラボラトリー（愛知県・名古屋市）
  • Year and Date: 2015-12-12
  • Invited
• [Presentation] ハロゲン化合物の酸化を基盤とする環境調和型分子変換法 (2015)
  • Author(s): 森山克彦
  • Organizer: 第９回化学系若手研究者講演会
  • Place of Presentation: 千葉大学亥鼻キャンパス（千葉県・千葉市）
  • Year and Date: 2015-12-11
  • Invited
• [Presentation] ニトロキシルラジカル触媒を用いたハロゲン結合活性化によるアミドとケイ素求核剤の酸化的カップリング反応 (2015)
  • Author(s): 倉持昌子、森山克彦、東郷秀雄
  • Organizer: 第70回記念有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 長岡工業高等専門学校（新潟県・長岡市）
  • Year and Date: 2015-11-21
• [Remarks] 精密有機反応化学研究室
  • URL: http://fineorgreact.chem.chiba-u.jp/presentations.html
• [Funded Workshop] International Congress on Pure & Applied Chemistry (ICPAC) 2018 (2018)
• [Funded Workshop] The 8th International Meeting on Halogen Chemistry (2017)