Development of Acyl and Silyl Group Transfer Reactions of Ketene Acetal Derivatives and Their Applications to the Synthesis of Natural Products

乙烯酮缩醛衍生物酰基和甲硅烷基转移反应的进展及其在天然产物合成中的应用

• 批准号: 61571002
• 负责人: KITA Yasuyuki
• 金额: $ 1.41万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 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/grant/KAKENHI-PROJECT-61571002/
• 关键词: Ketene acetal; Ketene silyl acetal; silyl-transfer reaction; Pummerer-type reaction; D-ribose; L-daunosamine; optically active nitrone; amino sugar; 分子内Pummever型反応; シリル基転位; Pummerer型反応; L-ダウノサミン

In organic synthesis, reagents are required which are able under neutral or nearly neutral conditions to bring about the desired reactions in high yields with easy isolation. For this purpose, ketene acetal derivatives 1 were suitably introduced as the reagents for alkoxycarbonylation, silylation, silylenation, carboxylic anhydride-formation, and the silyl group-transfer addition reactions from this laboratory.In connection with this study, we have established the synthesis of 2-deoxy-D-ribose from 2,3-O-isopropylidene-D-glyceraldehyde and N-benzoyl-1-daunosamine from (2)-[(4s)-trans-2,2,5-trimethyl-1,3-dioxolan-4-yl]methylene-[(1s)-1-phenylethyl]amine-N-oxide utilizing the silyl group-transfer addition reactions of o-silylated ketene acetal (1a). Furthermore, we have found that the treatment of sulfoxide with 1a caused a Pummerer-type rearrangement under nearly neutral conditions. As an extension of the reaction, we applied the reaction to a novel and efficient intramolecular Pummerer-type rearrangement of <omega>-amidosulfoxides which gave the 4 to 7-membered -thiolactams in high yields. Further studies on the annelation reactions of some sulfoxides haveing <omega>-olefinic substituents are in progress.

在有机合成中，需要能够在中性或接近中性条件下以高产率实现所需反应且易于分离的试剂。为此，本实验室适当引入乙烯酮缩醛衍生物 1 作为烷氧基羰基化、甲硅烷基化、甲硅烷基化、羧酸酐形成和甲硅烷基转移加成反应的试剂。结合本研究，我们已经建立了 2-脱氧-D-核糖的合成方法。 利用邻甲硅烷基化的甲硅烷基转移加成反应，从 (2)-[(4s)-反式-2,2,5-三甲基-1,3-二氧戊环-4-基]亚甲基-[(1s)-1-苯乙基]胺-N-氧化物得到 2,3-O-异丙叉-D-甘油醛和 N-苯甲酰基-1-道诺糖胺 乙烯酮缩醛(1a)。此外，我们发现用1a处理亚砜会在近中性条件下引起Pummerer型重排。作为该反应的延伸，我们将该反应应用于<omega>-酰胺亚砜的新颖且有效的分子内Pummerer型重排，从而以高产率产生4至7元硫内酰胺。对一些具有ω-烯属取代基的亚砜的稠合反应的进一步研究正在进行中。

项目成果

北泰行: 有機合成化学協会誌. 44. 1118-1133 (1986)

Yasuyuki Kita：有机合成化学学会杂志。44。1118-1133（1986）

北泰行: Chem.Pharm.Bull.35. 562-569 (1987)

喜多泰之：Chem.Pharm.Bull.35（1987）

北泰行: Tetrahedron Letters. 28. 1431-1434 (1987)

喜多康之：四面体信件 28. 1431-1434 (1987)

北泰行: J.Chem.Soc.,Chem.Commuu.(1988)

喜多康幸：J.Chem.Soc.、Chem.Commuu.(1988)

Yasuyuki Kita: "Development of Acyl and Silyl Group Transfer Reactions of Ketene Acetal Derivatives Utilizing Enol-Keto Tranformation and Their Applications to the Synthesis of Natural Products" Yakugaku Zasshi. 106. 269-285 (1986)

Yasuyuki Kita：“利用烯醇-酮转化开发乙烯酮缩醛衍生物的酰基和甲硅烷基转移反应及其在天然产物合成中的应用”Yakugaku Zasshi。