A Highly Efficient Synthesis of Cyclic Carbonyl Compounds via Acetylene-or Olefin-Titanium Complex

• Project/Area Number: 07651047
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: TOKYO INSTITUTE OF TECHNOLOGY
• Principal Investigator: OKAMOTO Sentaro TOKYO INSTITUTE OF TECHNOLOGY,Biosci.& Biotech., Assistant Professor, 生命理工学部, 助手 (00201989)
• Project Period (FY): 1995 – 1996
• Project Status: Completed (Fiscal Year 1996)
• Budget Amount: ¥1,700,000 (Direct Cost: ¥1,700,000); Fiscal Year 1996: ¥700,000 (Direct Cost: ¥700,000); Fiscal Year 1995: ¥1,000,000 (Direct Cost: ¥1,000,000)
• Keywords: Titanium / Cyclic ketone / Lactone / Low valent / Intramolecular / Nucleophilic acyl substitution / Enone / Cyclopropand / 有機チタン / 分子内求核アシル置換 / シクロアルカノン / α,β-不飽和ケトン / α,β-不飽和エステル

Research Abstract

Ti (O-i-Pr) 4/2i-PrMgBr reagent mediates the intramolecular nucleophilic acyl substitution (INAS) reactions of unsaturated compounds to afford organotitanium compounds containing functional groups. Because of the versatility of organotitanium compounds, the chemistry developed here provides an efficient, general method for the synthesis of butenolides, butanolides, vinyl cyclic ketones, alpha, beta-unsaturated ketones, and furans. Moreover, the reaction is practical, since the starting reagents, Ti (O-i-Pr) _4 and i-PrMgBr, are inexpensive and available in bulk, and the reaction procedure is operationally simple. Thus, the reaction would find widespread usage in synthetic organic chemistry.

Research Products

• [Publications] Aleksandr Kasatkin: "New,Efficient Method for the Synthesis of Allyltitanium Compounds from Allyl Halides or Allyl Alcohol Derivatives via Oxidative Addition. A Highly Efficient and Practical Synthesis of Homoallyl Alcohols 1" J.Am.Chem.Soc.117,13. 3881-3882 (1995)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Yasufumi Kawanaka: "Synthesis of the Key Component for Preparation of 6-Keto-prostaglandins by a Two-Component Coupling Process : Synthesis of 6-Keto-Prostaglandin E_1,Omoprostill and Δ^2-trans-6-Keto-Prostaglandin E_1." J.Chem.Soc.,Perkin Trans.1. 715-718 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by XTi(O-i-Pr)_3(X=Cl,O-i-Pr)/2i-PrMgBr Reagent. Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounds" J.Am.Chem.Soc.118,9. 2208-2216 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Aleksandr Kasatkin: "Synthesis of 1-Hydroxybicyclo[n.1.0]alkanes(n=3 and 4)and Their Silyl Ethers from Olefinic Esters via Tandem Intramolecular Nucleophilic Acyl Substitution and Intramolecular Carbonyl Addition Reactions Mediated by Ti(OPr-i)_4/2 i-PrMgCl Reagent" Tetrahedron Letters. 37,11. 1849-1852 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Sentaro Okamoto: "Highly Efficient Synthesis of Alka-1,3-dien-2-yltitanium Compounds from Alka-2,3-dienyl Carbonates. A New,Practical Synthesis of 1,3-Dienes and 2-Iodo-1,3-dienes" Tetrahedron Letters. 37,49. 8865-8868 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Yukio Yoshida: "Intramolecular Nucleophilic Acyl Substitution Reaction of 3,4-Alkadienyl Carbonates Mediated by Ti(O-i-Pr)_4/2i-PrMgCl Reagent. Efficient Synthesis of Optically Active β,γ-Unsaturated Esters with an α-Substituent" J.Org.Chem.61,22. 7826-7831 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Aleksandr Kasatkin: "New, Efficient Method for the Synthesis of Allyltitanium Compounds from Allyl Halides or Allyl Alcohol Derivatives via Oxidative Addition. A Highly Efficient and Practical Synthesis of Homoallyl Alcohols 1" J.Am.Chem.Soc.117,13. 3881-3882 (1995)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Yasufumi Kawanaka: "Synthesis of the Key Component for Preparation of 6-Keto-prostaglandins by a Two-Component Coupling Process : Synthesis of 6-Keto-Prostaglandin E_1, Ornoprostill and DELTA^2-trans-6-Keto-Prostaglandin E_1." J.Chem.Soc., Perkin Trans.1. 715-718 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by XTi (O-i-Pr)_3 (X=Cl, O-i-Pr) /2i-PrMgBr Reagent Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounds" J.Am.Chem.Soc.118,9. 2208-2216 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Aleksandr Kasatkin: "Synthesis of 1-Hydroxybicyclo [n.1.0] alkanes (n=3 and 4) and Their Silyl Ethers from Olefinic Esters via Tandem Intramolecular Nucleophilic Acyl Substitution and Intramolecular Carbonyl Addition Reactions Mediated by Ti (OPr-i)_4/2i-PrMgCl Reagent" Tetrahedron Letters. 37,11. 1849-1852 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Sentaro Okamoto: "Highly Efficient Synthesis of Alka-1,3-dien-2-yltitanium Compounds from Alka-2,3-dienyl Carbonates. A New, Practical Synthesis of 1,3-Dienes and 2-Iodo-1,3-dienes" Tetrahedron Letters. 37,49. 8865-8868 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Yukio Yoshida: "Intramolecular Nucleophilic Acyl Substitution Reaction of 3,4-Alkadienyl Carbonates Mediated by Ti (O-i-Pr)_4/2i-PrMgCl Reagent. Efficient Synthesis of Optically Active beta, gamma-Unsaturated Esters with an alpha-Substituent" J.Org.Chem.61,22. 7826-7831 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Yasufumi Kawanaka: "Synthesis of the Key Componert for Preparation of 6-Keto-prostaglandins by a Two-Component Coupling Process:Synthesis of 6-Keto-Prostaglandin E_1, Omoprostill and Δ^2-trans-6-Keto-Prostaglandin E_1." J.Chem.Soc.,Perkin Trans.1. 715-718 (1996)
• [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by XTi(O-i-Pr)_3(X=Cl,O-i-Pr)/2i-PnMgBr Reagent. Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounds" J.Am.Chem.Soc.118,9. 2208-2216 (1996)
• [Publications] Aleksandr Kasatkin: "Synthesis of 1-Hydroxybicyclo[n.1.0]alkanes(n=3 and 4)and Their Silyl Ethers from Olefinic Esters via Tandem Intramolecular Nucleophilic Acyi Substitution and Intramolecular Carbonyl Addition Reactions Mediated by Ti(OPr-i)_4/2i-PrMgCl Reagent" Tetrahedron Letters. 37,11. 1849-1852 (1996)
• [Publications] Sentaro Okamoto: "Highly Efficient Synthesis of Alka-1,3-dien-2-yltitanium Compounds from Alka-2,3-dienyl Carbonates. A New,Practical Synthesis of 1,3-Dienes and 2-Iodo-1,3-dienes" Tetrahedron Letters. 37,49. 8865-8868 (1996)
• [Publications] Yukio Yoshida: "Intramolecular Nucleophilic Acyl Substitution Reaction of 3,4-Alkadienyl Carbonates Mediated by Ti(O-i-Pr)_4/2 i-PrMgCl Reagent. Efficient syntheses of Optically Active β,γ-Unsaturated Esters with an α-Substituent" J.Org.Chem.61,22. 7826-7831 (1996)
• [Publications] Aleksandr Kasatkin: "Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by Ti(OP_<r-1>)_4/2i-PrMgBr Reacgent.Synthesis of Vinyltitanium Compounds Having a Lactone and/or an Ester Group from Acetylenic Carbonates" Tetrahedron Letters. 36. 6075-6078 (1995)
• [Publications] Sentaro Okamoto: "Intramolecular Nucleophilic Substitution Reactions Mediated by XTi(O_i-Pr)_3(X=Cl,O_i-Pr)/2i-PrMgBr Reagent.Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated Compounbds" Journal of American Chemical Society. 印刷中. (1996)