Development of Carbonylative Generation of Ketene and Its Application to the Synthesis of Useful Compounds

乙烯酮的羰基化生成及其在有用化合物合成中的应用

• 批准号: 05650859
• 负责人: OKUMOTO Hiroshi
• 金额: $ 1.41万
• 依托单位: Okayama 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: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05650859/
• 关键词: Carbonylation; allyl Phosphate; Palladium Catalyst; Ketene; Imine; beta-Lactam; Stereoselective Synthesis; 立体選択的反応

A new potential alkenylketene equivalent, prepared without use of a carboxylic acid or an activated derivative, has been exploited. Palladium-catalyzed carbonylation of an allyl phosphate in the presence of an imine and a tertiary amine under CO pressure (30Kgcm^<-2>) stereoselectively gave either a cis-or trans-3-alkeny1-beta-lactam in high yield. The stereochemical outcome strongly depends on the nature of the imine employed. Imines conjugated with a carbonyl such as a ketone or an ester stereoselectively produce cis-beta-lactams at room temperature, whereas imines unconjugated with a carbonyl group exclusively afford trans-beta-lactams at 70ﾟC.

一种新的潜在的烯基烯酮等价物，制备不使用羧酸或活化的衍生物，已被开发。在钯催化下，在亚胺和叔胺的存在下，在CO压力（30 Kgcm ^3）下，烯丙基磷酸酯的羰基<-2>化立体选择性地以高产率得到顺式或反式-3-烯基1-β-内酰胺。立体化学结果强烈地依赖于所用亚胺的性质。与羰基（如酮或酯）共轭的亚胺在室温下立体选择性地产生顺式-β-内酰胺，而未与羰基共轭的亚胺仅在70 ℃下产生反式-β-内酰胺。

项目成果

H.Tanaka: "2-Substituted Penems,New Candidates for Cephalosporinase Inhibitors" Bioorganic & Medicinal Chemistry Letters. 3. 2253-2254 (1993)

H.Tanaka：“2-取代青霉烯类，头孢菌素酶抑制剂的新候选者”生物有机

S.Torii: "Palladium-Catalyzed Sequential Bond Formation Leading to Conjugated Ene-Yne System" TETRAHEDRON LETT.34. 2139-2142 (1993)

S.Torii：“钯催化的顺序键形成导致共轭烯-Yne 系统”TETRAHEDRON LETT.34。

Sigeru Torii: "Carbonylative [2+2] Cycloaddition for the Construction of beta-Lactam Skeleton with Palladium Catalyst, Tetrahedron Lett." 34 (31). 6553-6556 (1993)

Sigeru Torii：“用钯催化剂构建β-内酰胺骨架的碳酰化 [2 2] 环加成反应，四面体莱特。”

S.Torii: "A Facile Conversion of 2-Substituted Acrylamides to 1,3-Disubstituted 3-Bromo-2-Azetidinones" SYNTH.COMMUN.23. 517-523 (1993)

S.Torii：“2-取代丙烯酰胺轻松转化为 1,3-二取代 3-溴-2-氮杂环丁酮”SYNTH.COMMUN.23。

Hideo Tanaka: "Palladium-catalyzed Carbonylative〔2+2〕Cycloaddition for the Stereoselective Synthesis of Either cis-or trans-3-Alkenyl-β-Lactams" J.Org.Chem.,. 59. 3040-3046 (1994)

Hideo Tanaka：“用于顺式或反式 3-烯基-β-内酰胺立体选择性合成的钯催化羰基化 [2+2] 环加成”J.Org.Chem., 59. 3040-3046 (1994)