Development of novel domino reaction utilizing feature of highly reactive imtermediate 'borylenamine'

2011 Fiscal Year Final Research Report

• Project/Area Number: 22790028
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Kobe Pharmaceutical University
• Principal Investigator: UEDA Masafumi 神戸薬科大学, 薬学部, 講師 (00340935)
• Project Period (FY): 2010 – 2011
• Keywords: 合成化学 / ラジカル反応 / 共役イミン

Research Abstract

Reagent dependent regioselective additions to dual activated alkyne have been developed. The reaction with alkyl radical afforded β-addition product, while the reaction with organocuprate gave α-adduct with both high regio-and stereoselectivities. These reactions were applied to domino and one-pot reaction, providing tetrasubstituted and functionalized alkenes. Computational studies have been demonstrated to rationalize the selectivity.

Research Products

• [Journal Article] Copper(II) Chloride-Mediated Cyclization Reaction of N-Alkoxy-ortho-alkynylbenzamides (2011)
  • Author(s): Jithunsa, M.; Ueda, M.; Miyata, O.
  • Journal Title: Org. Lett. Volume: 13(3) Pages: 518-521
• [Journal Article] Benzyl Radical Addition Reaction through the Homolytic Cleavage of a Benzylic C-H Bond (2011)
  • Author(s): Ueda, M.; Kondoh, E.; Ito, Y.; Shono, H.; Kakiuchi, M.; Ichii, Y.; Kimura, T.; Miyoshi, T.; Naito, T.; Miyata, O.
  • Journal Title: Org. Biomol. Chem. Volume: 9(7) Pages: 2062-2064
• [Journal Article] Silver-Catalyzed Synthesis of Disubstituted Isoxazoles by Cyclization of Alkynyl Oxime Ethers (2011)
  • Author(s): Ueda, M.; Ikeda, Y.; Sato, A.; Ito, Y.; Kakiuchi, M.; Shono, H.; Miyoshi, T.; Naito, T.; Miyata, O.
  • Journal Title: Tetrahedron Volume: 67(25) Pages: 4612-4615
• [Journal Article] Palladium-catalyzed Cross Coupling Reaction of N-Alkoxyimidoyl Bromides and Its Application to One-pot Synthesis of N-Arylamines (2011)
  • Author(s): Ueda, M.; Sugita, S.; Aoi, N.; Sato, A.; Ikeda, Y.; Miyoshi, T.; Naito, T.; Miyata, O.
  • Journal Title: Chem. Pharm. Bull. Volume: 59(9) Pages: 1206-1208
• [Journal Article] Regiodivergent Addition of Carbon Unit to Dual-Activated Alkynes for Stereoselective Construction of Tetrasubstituted Alkenes (2011)
  • Author(s): Ueda, M.; Matsubara, H.; Yoshida, K.; Sato, A.; Naito, T.; Miyata, O.
  • Journal Title: Chem. Eur. J. Volume: 17(6) Pages: 1789-1792
• [Journal Article] Direct Synthesis of Trisubstituted Isoxazoles through Gold-Catalyzed Domino Reaction of Alkynyl Oxime Ethers (2010)
  • Author(s): Ueda, M.; Sato, A.; Ikeda, Y.; Naito, T.; Miyata, O.
  • Journal Title: Org. Lett. Volume: 12(11) Pages: 2594-2597
• [Journal Article] Indium(I)-Mediated Radical Carbon-Carbon Bond-Forming Reaction in Aqueous Media (2010)
  • Author(s): Ueda, M.; Miyabe, H.; Torii, M.; Kimura, T.; Miyata, O.; Naito, T.
  • Journal Title: Synlett Volume: 9 Pages: 1341-1344
• [Journal Article] Synthesis of Fluorinated Imines by Addition of Fluoroalkyl Radicals to Conjugated Imines (2010)
  • Author(s): Ueda, M.; Iwasada, E.; Miyabe, H.; Miyata, O.; Naito, T.
  • Journal Title: Synthesis Volume: 12 Pages: 1999-2004
• [Journal Article] Efficient Entry into 2-Substituted Tetrahydroquinoline Systems through Alkylative Ring Expansion : Stereoselective Formal Synthesis of(±)-Martinellic Acid (2010)
  • Author(s): Ueda, M.; Kawai, H ; Hayashi, M.; Naito, T.; Miyata, O.
  • Journal Title: J. Org. Chem. Volume: 75(3) Pages: 914-921
• [Presentation] アルキニルN-アルコキシイミン類およびアミド類の遷移金属による閉環反応の開発 (2011)
  • Author(s): 上田昌史, Manita Jithunsa, 佐藤あおい, 三好哲也, 宮田興子
  • Organizer: 第37回反応と合成の進歩シンポジウム
  • Place of Presentation: 徳島
  • Year and Date: 2011-11-07
• [Presentation] ラジカル付加反応と[3, 3]-シグマトロピー転位が連動する新規ドミノ型反応の開発 (2011)
  • Author(s): 上田昌史, 伊藤勇太, 一井裕妃, 垣内麻衣子, 庄野裕子, 三好哲也, 宮田興子
  • Organizer: 第61回日本薬学会近畿支部総会・大会
  • Place of Presentation: 神戸
  • Year and Date: 2011-10-22
• [Presentation] Synthesis of Benzofuro [2, 3-b] pyrroles through a Radical Addition/ [3, 3]-Sigmatropic Rearrangement/Cyclization/Lactamization Cascade (2011)
  • Author(s): Masafumi Ueda, Yuta Ito, and Okiko Miyata
  • Organizer: 5th Pacific Symposium on Radical Chemistry
  • Place of Presentation: 和歌山
  • Year and Date: 2011-09-25
• [Presentation] ベンジル位のC-H結合開裂反応による炭素ラジカルの生成と電子不足オレフィンへの付加反応 (2010)
  • Author(s): 上田昌史, 近藤瑛子, 三好哲也, 内藤猛章, 宮田興子
  • Organizer: 第60回日本薬学会近畿支部総会・大会
  • Place of Presentation: 枚方
  • Year and Date: 2010-10-30
• [Presentation] Transition Metal-mediated Cyclization of N-Alkoxy-o-alkynylbenzamides for Chlorinated Heterocycles (2010)
  • Author(s): Jithunsa M., Ueda M., Miyata O.
  • Organizer: The 6th International Symposium on Integrated Synthesis
  • Place of Presentation: 神戸
  • Year and Date: 2010-10-24
• [Presentation] アルキニルオキシムエーテル類の遷移金属触媒を用いた閉環反応の開発:多置換イソキサゾール合成 (2010)
  • Author(s): 上田昌史, 佐藤あおい, 三好哲也, 内藤猛章, 宮田興子
  • Organizer: 第40回複素環化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2010-10-15
• [Presentation] Synthesis of Highly Substituted Isoxazoles through Transition Metal-Catalyzed Cyclization of Alkynyl Oxime Ethers (2010)
  • Author(s): Ueda M., Sato A., Miyoshi T., Naito T., Miyata O.
  • Organizer: The 18th International Conference on Organic Synthesis
  • Place of Presentation: Bergen
  • Year and Date: 2010-08-03