Development of new reactions based on the allene functionality and its application to natural product synthesis

• Project/Area Number: 21590008
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kanazawa University
• Principal Investigator: MUKAI Chisato 金沢大学, 薬学系, 教授 (70143914)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2010: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2009: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 合成化学 / 有機化学 / アレン / Pauson-Khand反応 / シクロプロパン / インドール / カルバゾール / Pauson-Khand型反応

Research Abstract

The following new reactions have been developed based on the allene functionality : i) Rh(I)-catalyzed cycloisomerization of bisallenes, ii) Rh(I)-catalyzed intramolecular[ 5+2] cycloaddition reaction of alkyne-allenylcyclopropanes, iii) intramolecular SN2'-type ring-closing reaction of 2-allenylaniline derivatives. In addition, several natural product syntheses have been accomplished using allene-based cyclization.

Research Products

• [Journal Article] Cu-Promoted[ 2+2] Cycloaddition of 1, 4-Bisallenes (2012)
  • Author(s): Kitagaki, S., Kajita, M., Narita, S., Mukai, C.
  • Journal Title: Org. Lett. Volume: 14 Issue: 6 Pages: 1366-1369
  • DOI: 10.1021/ol300096u
  • Peer Reviewed
• [Journal Article] Regioselective Intramolecular [3+2] Annulation of Allene-Nitrones (2012)
  • Author(s): Inagaki, F., Kobayashi, H., Mukai, C.
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 60 Issue: 3 Pages: 381-384
  • DOI: 10.1248/cpb.60.381
  • NAID: 130001852425
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed
• [Journal Article] Cu-Promoted [2+2] Cycloaddition of 1,4-Bisallenes (2012)
  • Author(s): Kitagaki, S
  • Journal Title: Org.Lett. Volume: 14 Pages: 1366-1369
  • Peer Reviewed
• [Journal Article] Rh(I)-Catalyzed[ 6+2] Cycloaddition of Alkyne-Allenylcyclobutanes : A New Entry for the Synthesis of Bicyclo[ 6. m. 0] Skeletons (2011)
  • Author(s): Inagaki, F., Sugikubo, K., Oura, Y., Mukai, C.
  • Journal Title: Chem. Eur. J. Volume: 17 Issue: 33 Pages: 9062-9065
  • DOI: 10.1002/chem.201101441
  • Peer Reviewed
• [Journal Article] A New Procedure for the Preparation of 2-Vinylindoles and Their[ 4+2] Cycloaddition Reaction (2011)
  • Author(s): Mohamed, Y. A. M., Inagaki, F., Takahashi, R., Mukai, C.
  • Journal Title: Tetrahedron Volume: 67 Issue: 29 Pages: 5133-5141
  • DOI: 10.1016/j.tet.2011.05.064
  • Peer Reviewed
• [Journal Article] Rh(I)-Catalyzed Intramolecular[ 2+2+1] Cycloaddition of Allenenes : Construction of Bicyclo[ 4. 3. 0] nonenones with an Angular Methyl Group and Tricyclo[ 6. 4. 0. 0^<1, 5]> dodecen one (2011)
  • Author(s): Inagaki, F., Itoh, N., Hayashi, Y., Matsui, Y., Mukai, C.
  • Journal Title: Beilstein J. Org. Chem. Volume: 7 Pages: 404-409
  • DOI: 10.3762/bjoc.7.52
  • Peer Reviewed
• [Journal Article] Total Syntheses of(-)-and(+)-Goniomitine (2011)
  • Author(s): Mizutani, M., Inagaki, F., Nakanishi, T., Yanagihara, C., Tamai, I., Mukai, C.
  • Journal Title: Org. Lett. Volume: 13 Issue: 7 Pages: 1796-1799
  • DOI: 10.1021/ol200320z
  • Peer Reviewed
• [Journal Article] Total Synthesis of(±)-Meloscine (2011)
  • Author(s): Hayashi, Y., Inagaki, F., Mukai, C.
  • Journal Title: Org. Lett. Volume: 13 Issue: 7 Pages: 1778-1780
  • DOI: 10.1021/ol200311y
  • Peer Reviewed
• [Journal Article] Can the Crabbe Homologation Be Successfully Applied to the Synthesis of 1, 3-Disubstituted Allenes (2011)
  • Author(s): Kitagaki, S. Komizu, M., Mukai, C.
  • Journal Title: Synlett Volume: 2011 Issue: 08 Pages: 1129-1132
  • DOI: 10.1055/s-0030-1259936
  • Peer Reviewed
• [Journal Article] Construction of Diverse Ring Systems Based on Allene-Multiple Bond Cycloaddition (2011)
  • Author(s): Inagaki, F., Kitagaki, S., Mukai, C.
  • Journal Title: Synlett Volume: 2011 Issue: 05 Pages: 594-614
  • DOI: 10.1055/s-0030-1259693
  • Peer Reviewed
• [Journal Article] Synthesis of Planar Chiral pseudo-ortho-Substituted Aryl[ 2. 2] paracyclophanes by Stepwise Successive Palladium-Catalyzed Coupling Reactions (2011)
  • Author(s): Kitagaki, S., Ohta, Y., Tomonaga, S., Takahashi, R., Mukai, C.
  • Journal Title: Tetrahedron : Asymmetry Volume: 22 Issue: 9 Pages: 986-991
  • DOI: 10.1016/j.tetasy.2011.05.023
  • Peer Reviewed
• [Journal Article] Construction of Diverse Ring Systems Based on Allene-Multiple Bond Cycloaddition (2011)
  • Author(s): Inagaki, F
  • Journal Title: Synlett Pages: 594-614
  • Peer Reviewed
• [Journal Article] Total Synthesis of (±)-Meloscine (2011)
  • Author(s): Hayashi, Y
  • Journal Title: Org.Lest. Volume: 13 Pages: 1778-1780
  • Peer Reviewed
• [Journal Article] Total Syntheses of (-)- and (+)-Goniomitine (2011)
  • Author(s): Mizutani, M
  • Journal Title: Org.Lett. Volume: 13 Pages: 1796-1799
  • Peer Reviewed
• [Journal Article] Total Syntheses of(+)-Fawcettimine and(+)-Lycoposerramine-B (2010)
  • Author(s): Otsuka, Y., Inagaki, F., Mukai, C.
  • Journal Title: J. Org. Chem. Volume: 75 Issue: 10 Pages: 3420-3426
  • DOI: 10.1021/jo100499h
  • Peer Reviewed
• [Journal Article] Chemistry of Allenic/Propargylic Anions Generated by Base Treatment of Sulfonylallenes : Synthesis of 1-Alkynyl-1-sulfonylcycloalkanes and Cycloalkanols (2010)
  • Author(s): Kitagaki, S., Teramoto, S., Ohta, Y., Kobayashi, H., Takabe, M., Mukai, C.
  • Journal Title: Tetrahedron Volume: 66 Issue: 21 Pages: 3687-3694
  • DOI: 10.1016/j.tet.2010.03.071
  • Peer Reviewed
• [Journal Article] Rhodium(I)-Catalyzed Intramolecular Carbonylative[ 2+2+1] Cycloadditionsand Cycloisomerizations of Bis(sulfonylallene) s (2010)
  • Author(s): Kawamura, T., Inagaki, F., Narita, S., Takahashi, Y., Hirata, S., Kitagaki, S., Mukai, C.
  • Journal Title: Chem. Eur. J. Volume: 16 Issue: 17 Pages: 5173-5183
  • DOI: 10.1002/chem.200903568
  • Peer Reviewed
• [Journal Article] Formal Synthesis of(+)-Nakadomarin A (2010)
  • Author(s): Inagaki, F., Kinebuchi, M., Miyakoshi, N., Mukai, C.
  • Journal Title: Org. Lett. Volume: 12 Issue: 8 Pages: 1800-1803
  • DOI: 10.1021/ol100412f
  • Peer Reviewed
• [Journal Article] Rhodium(I)-Catalyzed Intra-molecular[ 5+2] Cycloaddition Reactions of Alkynes and Allenylcycloprop-anes : Construction of Bicyclo[ 5. 4. 0] un-decatrienes and Bicyclo[ 5. 5. 0] dodeca-trienes (2010)
  • Author(s): Inagaki, F., Sugikubo, K., Miyashita, Y., Mukai, C.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 49 Issue: 12 Pages: 2206-2210
  • DOI: 10.1002/anie.200906994
  • Peer Reviewed
• [Journal Article] A New Entry for Preparation of 2-Substituted Azaindoles (2010)
  • Author(s): Shaykoon, M. S. A., Inagaki, F., Mukai, C.
  • Journal Title: Heterocycles Volume: 80 Issue: 1 Pages: 133-139
  • DOI: 10.3987/com-09-s(s)29
  • NAID: 40016900089
  • Peer Reviewed
• [Journal Article] Rhodium(I)-Catalyzed Intramolecular Carhonylative [2+2+1] Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s (2010)
  • Author(s): Kawamura, T
  • Journal Title: Chem.Eur.J. Volume: 16 Pages: 5173-5183
  • Peer Reviewed
• [Journal Article] Chemistry of Allenic/Propargylic Anions Generated by Base Treatment of Sulfonylallenes : Synthesis of 1-Alkynyl-1-sulfonylcycloalkanes and Cvcloalkanols (2010)
  • Author(s): Kitagaki, S
  • Journal Title: Tetrahedron Volume: 66 Pages: 3687-3694
  • Peer Reviewed
• [Journal Article] Total Syntheses of (+)-Fawcettimine and (+)-Lycoposerramine-B (2010)
  • Author(s): Otsuka, Y
  • Journal Title: J Org.Chem. Volume: 75 Pages: 3420-3426
  • Peer Reviewed
• [Journal Article] A New Entry for Preparation of 2-Substituted Azaindoles (2010)
  • Author(s): Shaykoon M.S.A
  • Journal Title: Heterocycles 80 Pages: 133-139
  • Peer Reviewed
• [Journal Article] Generation of N-(tert-Butoxy-carbonyl) indole-2, 3-quinodimethane and Its[ 4+2]-Type Cycloaddition (2009)
  • Author(s): Inagaki, F., Mizutani, M., Kuroda, N., Mukai, C.
  • Journal Title: J. Org. Chem. Volume: 74 Issue: 16 Pages: 6402-6405
  • DOI: 10.1021/jo901325d
  • Peer Reviewed
• [Journal Article] Synthesis of a Core Carbon Framework of Cyanosporasides A and B (2009)
  • Author(s): Aburano, D., Inagaki, F., Tomonaga, S., Mukai, C.
  • Journal Title: J. Org. Chem. Volume: 74 Issue: 15 Pages: 5590-5594
  • DOI: 10.1021/jo901141t
  • Peer Reviewed
• [Journal Article] Synthesis of a Core Carbon Framework of Cyanosporasides A and B (2009)
  • Author(s): Aburano, D
  • Journal Title: J.Org.Chem. 74 Pages: 5590-5594
  • Peer Reviewed
• [Journal Article] Generation of N-(tert-Butoxycarbonyl) indole-2, 3-quinodimethane and Its [4+2]-Type Cycloaddition (2009)
  • Author(s): Inagaki, F
  • Journal Title: J.Org.Chem. 74 Pages: 6402-6405
  • Peer Reviewed
• [Journal Article] Rhodium (I)-Catalyzed Intramolecular [5+2] Cycloaddition Reactions of Alkynes and Allenylcyclopropanes : Construction of Bicyclo [5.4.0] undecatrienes and Bicyclo [5.5.0] dodecatrienes (2009)
  • Author(s): Inagaki, F
  • Journal Title: Angew.Chem.Int.Ed. 4 Pages: 2206-2210
  • Peer Reviewed
• [Presentation] Serratineの合成研究 (2012)
  • Author(s): 畠山翔子
  • Organizer: 日本薬学会132年会
  • Place of Presentation: 北海道大学(北海道)
  • Year and Date: 2012-03-30
• [Presentation] アレニルシクロプロパンとアルケンとの立体選択的分子内環化付加反応 (2012)
  • Author(s): 向智里
  • Organizer: 日本薬学会132年会
  • Place of Presentation: 北海道大学(北海道)
  • Year and Date: 2012-03-29
• [Presentation] Rh(I)触媒を活用したアレン-アレニルシクロプロパンの環化付加反応 (2012)
  • Author(s): 川村行正
  • Organizer: 日本薬学会132年会
  • Place of Presentation: 北海道大学(北海道)
  • Year and Date: 2012-03-29
• [Presentation] ニトリルを反応成分とするPauson-Khand型反応の開発 (2012)
  • Author(s): 岩田隆
  • Organizer: 日本薬学会132年会
  • Place of Presentation: 北海道大学(北海道)
  • Year and Date: 2012-03-29
• [Presentation] (±)-Lycoflexine、(±)-Lycoposerramine-Qの全合成研究 (2011)
  • Author(s): 伊藤直哉
  • Organizer: 日本薬学会北陸支部123回例会
  • Place of Presentation: 金沢大学(石川)
  • Year and Date: 2011-11-27
• [Presentation] 銅塩/アミンを用いた1, 4-ビスアレンの[ 2+2]環化付加反応 (2011)
  • Author(s): 梶田幹人
  • Organizer: 日本薬学会北陸支部123回例会
  • Place of Presentation: 金沢大学(石川)
  • Year and Date: 2011-11-27
• [Presentation] (+)-Indicanoneの全合成研究 (2011)
  • Author(s): 小川久美子
  • Organizer: 日本薬学会北陸支部123回例会
  • Place of Presentation: 金沢大学(石川)
  • Year and Date: 2011-11-27
• [Presentation] 銅塩を用いた1-アルキン,アルデヒド,アミンの三成分連結反応を経る1, 3-二置換アレンの合成 (2011)
  • Author(s): 小水美佳
  • Organizer: 日本薬学会北陸支部123回例会
  • Place of Presentation: 金沢大学(石川)
  • Year and Date: 2011-11-27
• [Presentation] 銅塩/アミンを用いた1,4-ビスアレンの[2+2]環化付加反応 (2011)
  • Author(s): 梶田幹人
  • Organizer: 日本薬学会北陸支部123回例会
  • Place of Presentation: 金沢大学(石川)
  • Year and Date: 2011-11-27
• [Presentation] 銅塩を用いた1-アルキン,アルデヒド,アミンの三成分連結反応を経る1,3-二置換アレンの合成 (2011)
  • Author(s): 小水美佳
  • Organizer: 日本薬学会北陸支部123回例会
  • Place of Presentation: 金沢大学(石川)
  • Year and Date: 2011-11-27
• [Presentation] (±)-Lycoflexineの全合成研究 (2011)
  • Author(s): 伊藤直哉
  • Organizer: 第41回複素環化学討論会
  • Place of Presentation: 崇城大学市民ホール(熊本)
  • Year and Date: 2011-10-22
• [Presentation] Rhodium(I)-Catalyzed Cycloisomerization of Bis(phenylsulfon-ylallene) s (2011)
  • Author(s): Kawamura, T.
  • Organizer: 23rd International Congress of Heterocyclic Chemistry
  • Place of Presentation: Glasgow(UK)
  • Year and Date: 2011-08-01
• [Presentation] Total Synthesis of(±)-Meloscine (2011)
  • Author(s): Hayashi, Y.
  • Organizer: 23rd International Congress of Heterocyclic Chemistry
  • Place of Presentation: Glasgow(UK)
  • Year and Date: 2011-08-01
• [Presentation] Rhodium(I)-Catalyzed Cycloisomerization of Bis (phenylsulfonylallene)s (2011)
  • Author(s): Kawamura, T.
  • Organizer: 23rd International Congress of Heterocyclic Chemistry
  • Place of Presentation: Glasgow (UK)
  • Year and Date: 2011-08-01
• [Presentation] Total Synthesis of (±)-Meloscine (2011)
  • Author(s): Hayashi, Y.
  • Organizer: 23rd International Congress of Heterocyclic Chemistry
  • Place of Presentation: Glasgow (UK)
  • Year and Date: 2011-08-01
• [Presentation] (±)-Meloscineの全合成 (2010)
  • Author(s): 林佑次郎
  • Organizer: 日本薬学会北陸支部第122回例会
  • Place of Presentation: 北陸大学(石川)
  • Year and Date: 2010-11-21
• [Presentation] 多置換型ビスアレンを用いたRh(I)触媒分子内Pauson-Khand型反応の開発 (2010)
  • Author(s): 高橋康仁
  • Organizer: 日本薬学会北陸支部第122回例会
  • Place of Presentation: 北陸大学(石川)
  • Year and Date: 2010-11-21
• [Presentation] A New Entry for Generation of 2-Vinylindoles and Their[ 4+2]-Type Cycloaddition (2010)
  • Author(s): Yaseen Mohamed
  • Organizer: 日本薬学会北陸支部第122回例会
  • Place of Presentation: 北陸大学(石川)
  • Year and Date: 2010-11-21
• [Presentation] (±)-Meloscineの全合成 (2010)
  • Author(s): 林佑次郎
  • Organizer: 日本薬学会北陸支部第122回例会
  • Place of Presentation: 北陸大学薬学部(石川県)
  • Year and Date: 2010-11-21
• [Presentation] 多置換型ビスアレンを用いたRh(I)触媒分子内Pauson-Khand型反応の開発 (2010)
  • Author(s): 高橋康仁
  • Organizer: 日本薬学会北陸支部第122回例会
  • Place of Presentation: 北陸大学薬学部(石川県)
  • Year and Date: 2010-11-21
• [Presentation] A New Entry for Generation of 2-Vinylindoles and Their[4+z]-Type Cycloaddition (2010)
  • Author(s): Yaseen Mohamed
  • Organizer: 日本薬学会北陸支部第122回例会
  • Place of Presentation: 北陸大学薬学部(石川県)
  • Year and Date: 2010-11-21
• [Presentation] アレンを基盤とする中員環含有双環性骨格の新規構築 (2010)
  • Author(s): 稲垣冬彦
  • Organizer: 第36回反応と合成の進歩シンポジウム
  • Place of Presentation: ウインクあいち(愛知)
  • Year and Date: 2010-11-01
• [Presentation] アレンを基盤とする中員環含有双環性骨格の新規構築 (2010)
  • Author(s): 稲垣冬彦
  • Organizer: 第36回反応と合成の進歩シンポジウム
  • Place of Presentation: ウインクあいち(愛知県)
  • Year and Date: 2010-11-01
• [Presentation] Goniomitineの不斉全合成研究 (2010)
  • Author(s): 水谷仁弥
  • Organizer: 第40回複素環化学討論会
  • Place of Presentation: 仙台市民会館(宮城)
  • Year and Date: 2010-10-15
• [Presentation] Goniomitineの不斉全合成研究 (2010)
  • Author(s): 水谷仁弥
  • Organizer: 第40回複素環化学討論会
  • Place of Presentation: 仙台市民会館(宮城県)
  • Year and Date: 2010-10-15
• [Presentation] Pauson. Khand反応を活用した効率的な多環状天然物の合成:(±)-meloscine及び(+)-nakado-marin Aの全合成 (2010)
  • Author(s): 稲垣冬彦
  • Organizer: 第8回次世代を担う有機化学シンポジウム
  • Place of Presentation: 日本薬学会長井記念ホール(東京)
  • Year and Date: 2010-05-14
• [Presentation] Pauson-Khand反応を活用した効率的な多環状天然物の合成:(土)-mekloscine及び(+)-nukadomarinAの全合成 (2010)
  • Author(s): 稲垣冬彦
  • Organizer: 第8回次世代を担う有機化学シンポジウム
  • Place of Presentation: 日本薬学会長井記念ホール(東京都)
  • Year and Date: 2010-05-14
• [Presentation] Rh (I) 触媒を活用したアルキン・アレニルシクロプロパンの [5+2] 環化付加反応 (2010)
  • Author(s): 杉窪克哉
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学 (岡山県)
  • Year and Date: 2010-03-30
• [Presentation] ビスアレンを活用した新規Rh^I触媒中員環構築法の開発 (2010)
  • Author(s): 川村行正
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学 (岡山県)
  • Year and Date: 2010-03-30
• [Presentation] (±)-Goniomitineの全合成研究 (2010)
  • Author(s): 水谷仁弥
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学(岡山)
  • Year and Date: 2010-03-28
• [Presentation] Rh(I)触媒を活用したアルキン-アレニルシクロプロパンの[ 5+2]環化付加反応 (2010)
  • Author(s): 杉窪克哉
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学(岡山)
  • Year and Date: 2010-03-28
• [Presentation] ビスアレンを活用した新規Rh^I触媒中員環構築法の開発 (2010)
  • Author(s): 川村行正
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学(岡山)
  • Year and Date: 2010-03-28
• [Presentation] (±)-Goniomitine の全合成研究 (2010)
  • Author(s): 水谷仁弥
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学 (岡山県)
  • Year and Date: 2010-03-28
• [Presentation] Total Stntheses of Nakado-marin A and Meloscine Based on Pauson-Khand Reaction (2009)
  • Author(s): Mukai, C.
  • Organizer: Catalysis and Fine Chemicals 2009
  • Place of Presentation: Korea University(Korea)
  • Year and Date: 2009-12-16
• [Presentation] Total Stntheses of Nakadomarin A and Meloscine Based on Pauson-Khand Reaction (2009)
  • Author(s): Mukai, C
  • Organizer: Catalysis and Fine Chemicals 2009
  • Place of Presentation: Korea University (Korea)
  • Year and Date: 2009-12-16
• [Presentation] (±)-Meloscineの全合成研究 (2009)
  • Author(s): 林佑次郎
  • Organizer: 第39回複素環化学討論会
  • Place of Presentation: さわやか千葉県民プラザ(千葉)
  • Year and Date: 2009-10-14
• [Presentation] (±)-Meloscine の全合成研究 (2009)
  • Author(s): 林佑次郎
  • Organizer: 第39回複素環化学討論会
  • Place of Presentation: さわやか千葉県民プラザ (千葉県)
  • Year and Date: 2009-10-14
• [Presentation] (±)-Meloscine の全合成研究 (2009)
  • Author(s): 林佑次郎
  • Organizer: 平成21年度有機合成化学北陸セミナー
  • Place of Presentation: 富山観光ホテル (富山県)
  • Year and Date: 2009-10-09
• [Presentation] ビスアレンを活用した新規中員環構築 (2009)
  • Author(s): 川村行正
  • Organizer: 平成21年度有機合成化学北陸セミナー
  • Place of Presentation: 富山観光ホテル (富山県)
  • Year and Date: 2009-10-09
• [Presentation] インドール-2, 3-キノジメタンの新規発生法の開発及びその [4+2] 型環化付加反応 (2009)
  • Author(s): 水谷仁弥
  • Organizer: 平成21年度有機合成化学北陸セミナー
  • Place of Presentation: 富山観光ホテル (富山県)
  • Year and Date: 2009-10-09
• [Presentation] Rh (I) 触媒を活用したアルキン-アレニルシクロプロパンの [5+2] 型環化付加反応 (2009)
  • Author(s): 杉窪克哉
  • Organizer: 平成21年度有機合成化学北陸セミナー
  • Place of Presentation: 富山観光ホテル (富山県)
  • Year and Date: 2009-10-09