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，需要在中性或几乎中性条件下以易于分离的高产率带来所需反应的试剂。为此，适当地引入了酮乙烯衍生物1，作为烷氧基钙化的试剂，甲硅烷基化，冲突，硅胶化，羧基赤道酸酯形式和Silyl群组转移反应，与这项实验室的联系。来自（2） - [（（4S） - Trans-2,2,5-二甲基-1,3-二氧烷-4-4-4-甲基]甲基 - （1S） - （1S） - 1-1-苯基甲基甲基甲基化的氧化氨基化的ORIMINGLINLLINLLTRATCRATTRARTRATRATRATRATRATRATIONL的2,3-O-异丙基甘油醛和N-苯唑1-1-氨基胺和N-苯甲酰1-羟胺 - [（4S）-Trans-2,2,5-三甲基-1,3-二氧二氧糖-4-4-4-4-基]甲基 - （1S） - （1S） - 1-1-1-菲尼甲基甲基甲基氨基甲基氨基化的反应。酮乙烯（1A）。此外，我们发现用1A的硫氧化物治疗在几乎中立的条件下导致pummer型重排。作为反应的扩展，我们将反应应用于<Omega> - 氨基硫代的新型且有效的分子内pummer型重排，该重排在高产量中给出了4至7元的硫代酰胺。进一步研究了一些具有<欧米茄> - 奥仪取代基的亚氧化亚氧化氧化物的反应。

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

喜多康之：四面体信件 28. 1431-1434 (1987)

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

喜多泰之：Chem.Pharm.Bull.35（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。