Asymmetric Synthesis of Usseful Natural Products by Means of Organosilicon Compounds

利用有机硅化合物不对称合成有用的天然产物

• 批准号: 07454164
• 负责人: ITO Yoshihiko
• 金额: $ 5.06万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454164/
• 关键词: 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

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.

我们已经报道了光学活性的3-(1，4-戊二烯基)苯甲基二硅氧烷在钯(叔烷基异氰基)络合物催化下的高非对映选择性分子内双硅烷基化反应，高产率地合成了3(R)，4(R)，5(R)-三取代的2-硅四氢呋喃。指出了分子内双硅烷化反应中高度可控的非对映界面选择。合成的(R，R，R)-2-四氢呋喃用于全合成(-)-燕麦内酯的合成方法如下。Rh催化5元(R，R，R)-2-硅烷四氢呋喃上的乙烯基的区域选择性氢化反应，然后氧化得到相应的伯醇。接下来，两个硅-碳键被氧化裂解，在保留立体化学的情况下转化为相应的醇。经过适当的保护和去保护，伯醇在酸性条件下被氧化成相应的双内酯。最后，内酯环上的选择性亚甲基化得到(-)-文奈酯内酯。本研究中的(-)-艾维奈酯的全合成为基于硅碳键的立体选择性构筑提供了一条新的有效途径。硅碳键是羟基的合成等价物。

项目成果

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)

杉目道典：“碳-碳双键的非对映选择性分子内双硅烷化。(-)-燕麦内酯的高度立体控制合成”J.Amer.Chem.Soc.117・37 (1995)。

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)

Yoshihiko Ito：“Si-Si б-键与双（t-烷基异氰化物）钯（o）络合物的还原。环状双（有机甲硅烷基）钯络合物的合成和反应”公报，日本。 299 (1996)

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)

Michinori Suginome：“有机硅大环的合成。通过 Si-Si σ-键复分解的钯催化环乙硅烷的扩环低聚”有机金属学 15・8。

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)

伊藤义彦：“碳-碳双键的非对映选择性分子内双硅烷化。(-)·Avenociolide 的高度立体控制合成”J. Am. 9608-9609。

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)

伊藤义彦：“钯(0)叔烷基异氰化物络合物催化的烯烃分子内双硅烷化多元醇的立体选择性合成”Pure & Appl.Chem.68・3 (1996)。