Organic Synthesis Using Highly Strained Cyclopropenyl Cations

• Project/Area Number: 05650885
• Research Category: Grant-in-Aid for General Scientific Research (C)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: OSAKA PREFECTURE UNIVERSITY
• Principal Investigator: INOUE Hiroo Osaka Prefecture University, College of Engineering Professor, 工学部, 教授 (10081316)
• Co-Investigator(Kenkyū-buntansha): MATSUMURA Noboru Osaka Prefecture Universty, College of Engineering, Research Associate, 工学部, 助手 (40125274) ; HARUKI Eiichi Osaks Prefecture Universty, College of Engineering, Lecture, 工学部, 講師 (90081322)
• Project Period (FY): 1993 – 1994
• Project Status: Completed (Fiscal Year 1994)
• Budget Amount: ¥2,200,000 (Direct Cost: ¥2,200,000); Fiscal Year 1994: ¥500,000 (Direct Cost: ¥500,000); Fiscal Year 1993: ¥1,700,000 (Direct Cost: ¥1,700,000)
• Keywords: Cycopropenyl Cation / Thiophene Derivatives / Pyrole Derivatives / alpha, beta-Unsaturated Carbonyl Compounds / シクロプロペニルカチオン類 / ピリジン誘導体 / 縮合ヘテロ環系化合物 / alpha,beta-不飽和カルボン酸類

Research Abstract

Tris (isopropylthio) cyclopropenylium perchlorate (1) is a useful three-carbon building block in organic synthesis. The results our obtained are summarized below.
1) Tris (isopropyltho) cyclopropenylium perchlorate (1) reacts with potassium dithiocarbamates to give thiophene derivatives in good yield.
2) Tris (isopropylthio) cyclopropenylium perchlorate (1) reacts with sodium arylsulfinates in dry acetonitlile and benzene under reflux to give arylsulfinylpropenethioates in good yield.
accompanied by the formation of arylsulfonylallenes, through cyclopropene intermediates and then vinylcarbene,
3) The reaction of tris (isopropylthio) cyclopropenylium perchlorate (1) with alpha-Lithiated tosylmethyl, benzyl and benzoylmethyl isocyanides in dry tetrahydrofuran gave the pyridine deribatives, respectively.

Research Products

• [Publications] Hideo Kojima: "A New Route to Pyridine Derivatives by the Reaction of Tris(isopropylthio)-cyclopropenylium Perchlorate with alpha-Lithiated Isocyanides" J.Heterocyclic Chemistry. 30. 1691-1692 (1993)
• [Publications] Hideo Kojima: "Intramolecular Transfer of Sulfonyl Oxygen to Vinylcarbene Generated in the Reaction of Tris(isopropylthio)cyclopropenyl Cation with Arylsulfinate Salts" J.Chem.Soc.,Chem.Commun. 1674-1676 (1993)
• [Publications] Hideo Kojima: "New Organic Reactions using Cyclopropenyl Cations as a Three-carbon Building Block" 3rd Tohwa Univ.Int.Symp.Proc.235 (1993)