Asymmetric Synthesis of Usseful Natural Products by Means of Organosilicon Compounds

• Project/Area Number: 07454164
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: KYOTO UNIVERSITY
• Principal Investigator: ITO Yoshihiko Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (40026018)
• Co-Investigator(Kenkyū-buntansha): SUGINOME Michinori Kyoto University, Graduate School of Engineering, Instructor, 工学研究科, 助手 (60252483)
• Project Period (FY): 1995 – 1996
• Project Status: Completed (Fiscal Year 1996)
• Budget Amount: ¥7,900,000 (Direct Cost: ¥7,900,000); Fiscal Year 1996: ¥2,200,000 (Direct Cost: ¥2,200,000); Fiscal Year 1995: ¥5,700,000 (Direct Cost: ¥5,700,000)
• Keywords: Bis-silylation of olefins / Palladium tert-alkyl isocyanide complex / Avenaciolide / Organosilicon Compounds / Oxidative Cleavage of Carbon-silicon Bonds / Intramolecular Bis-silylation / アベノシオリドの全合成 / ビス・シリル化反応 / オレフィンの分子内ビス・シリル化 / パラジウム(o)イソシアニド錯体 / パラジウム・第三級アルキルイソニトリル錯体

Research Abstract

We have previouly described highly diastereoselective intramolecular bissilylation of optically active 3- (1,4-pentadienyl) phenylmethyl disilanylether catalyzed by palladium (tert-alkylisocyanide) complex, producing 3 (R), 4 (R), 5 (R) -trisubstituted 2-silatetrahydrofuran in high yield. The highly controlled diastereoface selection in the intramolecular bis-silylation is remarked. The (R,R,R) -2-silatetrahydrofuran thus prepared was synthetically elaborated for total synthesis of (-) -avenaciolide as follows. Rhodium catalyzed regioselective hydroboration of the vinyl group on the five membered (R,R,R) -2-silatetrahydrofuran was followed by oxidation to give the corresponding primary alchohol. Next, the two silicon-carbon bonds were oxidatively cleaved to convert to the corresponding alchohols with retention of stereochemistry. After appropriate protection and then deprotection, the primary alcohols were oxidized to give the corresponding bis-lactone under acidic condition. Finally, selective methylenation on the lactone ring furnished (-) -Avenaciolide. The total synthesis of (-) -Avenaciolide in this research presented a new and efficient approach on the basis of stereoselective construction of silicon-carbon bonds, which are synthetic equivalents to hydroxy groups.

Research Products

• [Publications] Yoshihiko Ito: "Intramolecular Bis-silylation of Alkenes Catalyzed by Palladium(0) tert-Alkyl Isocyanide Complex Stereoselective Synthesis of Polyols" Pure & Appl.Chem.68・3. 505-508 (1996)
• [Publications] Michinori Suginome: "Synthesis of Organosilicon Macrocycles. Palladium-Catalyzed Ring-Enlargement Oligomerization of Cyclic Disilanes via Si-Si σ-Bond Metathesis" Organometallics. 15・8. 2170-2178 (1996)
• [Publications] Michinori Suginome: "Disilanyl Group as a Synthetic Equivalent of the Hydroxyl Group" Synlett. 941-942 (1995)
• [Publications] Michinori Suginome: "Diastereoselective Intramolecular Bis-silylation of a Carbon-Carbon Double Bond. A Highly Stereocontrolled Synthesis of(-)-Avenaciolide" J.Amer.Chem.Soc.117・37. 9608-9609 (1995)
• [Publications] Yoshihiko Ito: "Diastereoselective Intramolecular Bis-silylation of a Carbon-Carbon Double Bond. A Highly Stereocontrolled Synthesis of (-)・Avenociolide" J. Am. Chem. Soc.117. 9608-9609 (1995)
• [Publications] Yoshihiko Ito: "Reuctions of Si-Si б-Bonds with Bis(t-alkyl isocyanide) palladium(o) Complexes. Synthesis and Reactions of Cyclic Bis(organosilyl) palladium Complexes" Bull. Chem. Soc. Japan. 69. 289-299 (1996)