Studies on a Novel Dehydrationg Gent, (Trimethylsilyl)ethoxyavetylene

新型脱水剂（三甲基硅基）乙氧基乙炔的研究

• 批准号: 61870086
• 负责人: TAMURA Yasumitsu
• 金额: $ 1.98万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61870086/
• 关键词: dehydtaing agent; acid anhydride reagent; homophtalic anhydride; (trimethylsilyl)ethoxyacetylens; (trimethlsilyl)ketene; <alpha>-(trimethlsilyl)aceteta; d-(トリメチルシリ)アセタート; 分子内Peterson反応

We have found that (trimethylasilyl)ethoxyacetlene (TMEA) provided a quire effective method for dehydration of various types of carboxylic acids, including acids-sensitive catboxylic acide into the corresponding carboxylic anhydrides under nmild conditions, and allowed easy isolation of pure products. These carboxylic anhydrides were successfully utilized for the strong base-induced cycloaddition to naphthoquinones leading to anthracyclines. We also succeeded in applying this carboxyl group activating method to the synthesis of amides.The following progress was made in the present project. We suvveeded in the first total sysnthesis of D-rind thiophene and indole analogues of daunomycin via a stronf-base induced cycloaddition of hterohomophthalic anhydride obtained by the use of TMEA. The reagent, TMEA was found to useful not only for amide formation but also for ewster, lactone, or non-racemized peptide formation. Next, we founs thar teimethylsilyl ketene (TMSK), readily prepared by heating of TMEA under reduced pressure, reacted with vatious types of alconhols to give the 1,2addition products, a-(trimethylsilyl)acetates in quantitative yield. The alcohol having carbonyl group in the moleuce similarly reacted with TMSK to give the corresponfding <alpha>-(trimethylsilyl)acetate, which caused an intramolcular pererson reaction to five <alpha>,<beta>-unsaturated lactone in excellent yield. We now try to find a novel annelation reaction using various types of <alpha>-(trimethylsilyl)acetates obtained by treatment of alcohols having some active functional gqoup with TMSK.

我们发现，（三甲基甲硅烷基）乙氧基乙炔（TMEA）提供了一个非常有效的方法，用于脱水的各种类型的羧酸，包括酸敏感的羧酸为相应的羧酸酐在温和的条件下，并允许容易地分离纯产品。这些羧酸酐被成功地用于强碱诱导的萘醌环加成反应，导致蒽环类。本课题还成功地将这种羧基活化方法应用于酰胺类化合物的合成，取得了以下进展。我们首次报道了利用TMEA通过强碱诱导的杂高邻苯二甲酸酐环加成反应合成了柔红霉素的D-皮噻吩和吲哚类似物。发现试剂TMEA不仅可用于酰胺形成，而且可用于酯、内酯或非外消旋肽的形成。然后，我们发现，由TMEA在减压下加热容易制备的四甲基硅基烯酮（TMSK）与各种醇反应，以定量产率得到1，2加成产物α-（三甲基硅基）乙酸酯。分子中含有羰基的醇与TMSK反应生成相应<alpha>的-（三甲基硅基）乙酸酯，并在分子内发生质子交换反应，以高产率生成5<alpha>，<beta>-不饱和内酯。我们现在试图找到一种新的缩合反应，使用不同类型的<alpha>-（三甲基硅基）乙酸酯，通过处理醇具有一些活性功能团与TMSK。

项目成果

田村 恭光: J. Chem. Soc. Chem. Commun,. 1474-1476 (1987)

田村康光：化学学会，1474-1476（1987）

北 泰行: J. Org. Chem,. 51. 4150-4158 (1986)

喜多康幸：《有机化学》，51。4150-4158（1986）

田村 恭光: Tetrahedron Letters. 28. 3971-3974 (1987)

田村康光：《四面体信件》28。3971-3974 (1987)

北 泰行: Tetrahedrou Letters. (1988)

喜多康之：四面体信件 (1988)

Yasumitsu Tamura, Hasayuki Kirihara, Jun-ichi Sekihachi, Ryuichi Okunaka, Shin-ichito Mohri, Teruhisa Tsugoshi, Shuji Akai, Manabe Saasho, Yasuyuki Kita: "A new synthetic stragegy for Heteroanthracyclined: Total Synthesis of D-Ring Thiophene Analogs of Da

Yasumitsu Tamura、Hasayuki Kirihara、Jun-ichi Sekihachi、R​​yuichi Okunaka、Shin-ichito Mohri、Teruhisa Tsugoshi、Shuji Akai、Manabe Saasho、Yasuyuki Kita：“杂蒽环化合物的新合成策略：Da 的 D 环噻吩类似物的全合成