Development of transformations of bicyclic compounds to monocyclic compounds through sequential bond cleavage

2018 Fiscal Year Final Research Report

• Project/Area Number: 16K05783
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Tokyo University of Science
• Principal Investigator: Matsuda Takanori 東京理科大学, 理学部第一部応用化学科, 准教授 (80359778)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Keywords: 環化 / 骨格転位 / アリール化 / ロジウム / シクロプロペノン / カルボニル化 / 開環

Outline of Final Research Achievements

In this study, research on catalytic transformations of bicyclic compounds to monocyclic compounds through sequential bond cleavage was conducted, and sevaral reactions were developed. Rh-catalyzed skeletal rearrangements of benzofused spiro[3.3]heptanes gave substituted naphthalenes. Rh-catalyzed carbonylation of (2-pyridylmethylene)cyclobutanes gave five-membered cyclic ketones. Pd-catalyzed ring-opening coupling of cyclobutenols with aryl halides gave γ-arylated α,β-unsaturated ketones. 2-[(2-Azidophenyl)ethynyl]anilines cyclized by Au/Rh relay catalysis to give 5,10-dihydroindolo[3,2-b]indoles. Ag-catalyzed ring-opening [3+2] annulation of cyclopropenones with amides gave 5-amino-2-furanones. Rh-catalyzed addition of arylboronic acids to β-(arylethynyl) ketones gave (arylmethyl)naphthalenes. Ru-catalyzed cycloisomerization of 1,2-bis(2-allylphenyl)ethynes gave 2,2′-dimethyl-3H,3′H-1,1′-biindenes, and tandem RCM of the diynes gave 2,2′-unsubstituted biindenes.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

環歪みを有しユニークな反応性を示すシクロブタン、シクロブテン、シクロプロペン誘導体の新しい遷移金属触媒反応を開発することができた。また、連続的な結合切断反応の持つ合成化学的な有用性を示すこともできた。今後、機能性π共役分子の選択的合成などに応用されることが期待される。さらに、遷移金属触媒による炭素骨格再構築反応の可能性、現時点での課題、および今後の展望についても有益な情報を得ることができた。