Generation of Reactive Species Acyl Lithium and Its Reactions

活性物质酰基锂的生成及其反应

• 批准号: 05403027
• 负责人: MURAI Shinji
• 金额: $ 26.24万
• 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 (A)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05403027/
• 关键词: Acyllithium; Cerbon Monoxide; Trimethylsilyldizaomethane; Silylynolate; シリルジアゾメタン; ジシリルケテン; カルバモイルリチウム; 転位; 環化; β-脱離; カルバモイルシラン; [4+1]シクロカップリング; Acyllithium; Cerbon Monoxide; Trimethylsilyldizaomethane; Silylynolate; シリルジアゾメタン; ジシリルケテン; カルバモイルリチウム; 転位; 環化; β-脱離; カルバモイルシラン; [4+1]シクロカップリング

1. Generation and reactions of carbonyl anions, relatively unknown species, have been studied. The reaction of beta-phenyl-2-azaethenyllithium, generated from aryl isocyanides and t-BuLi, with carbon monoxide gives 3H-indole derivatives in 42-44% yields after quenching with MeI.Similarly, beta-phenyl-1-azaethenyllithium, obtainable by the addition of alkyllithium to benzonitriles, reacts with carbon monoxide and MeI to afford 1H-isoindole derivatives in 73-81% yields. A 1,4-diazabutadienyl anion gives a cyclic urea on reaction with carbon monoxide and MeI.These reactions represent novel [4+1] cyclocoupling reactions of dienyl anions with carbon monoxide via carbonyl anions as the intermediates.2. The reaction of lithiotrimethylsilyldiazomethane, generated from treatment of trimethylsilyldiazomethane with BuLi at -78ﾟC,with carbon monoxide at -78ﾟC followed by quenching with triethylsilyl trifluoromethanesulfonate (Et_3SiOTf) affords a bissilylketene in 85% yield. The reaction proceeds via a silylynolate which is formed by extrusion of N_2 from the carbonyllithium. The silylynolate act as ketenylation reagent. The silylynolate is found to react with carbon electrophiles such as oxiranes and ethyl benzalmalonate in the presence of equimolar amount of Me_3Al. The treatment of silylynolate with cyclohexene oxide gave a lactone via ring-opeming ketenylation followed by intramolecular cyclization. These reactions are first examples that silylynolate was trapped by carbon electrophiles.

1。羰基阴离子的产生和反应，相对未知物种，已经研究了。 The reaction of beta-phenyl-2-azaethenyllithium, generated from aryl isocyanides and t-BuLi, with carbon monoxide gives 3H-indole derivatives in 42-44% yields after quenching with MeI.Similarly, beta-phenyl-1-azaethenyllithium, obtainable by the addition of alkyllithium to benzonitriles, reacts with carbon monoxide and MEI以73-81％的收益率提供1His-Indole衍生物。 1,4-二唑二氮基阴离子在与一氧化碳和MEI反应时产生环状尿素。这些反应代表二烯基阴离子与一氧化碳通过羰基阴离子作为中间体的新型[4+1]环偶化反应。2。 The reaction of lithiotrimethylsilyldiazomethane, generated from treatment of trimethylsilyldiazomethane with BuLi at -78ﾟC, with carbon monoxide at -78ﾟC followed by quenching with triethylsilyl trifluoromethanesulfonate (Et_3SiOTf) affords a bissilylketene in 85% yield.反应通过甲硅烷基酸盐进行，该甲硅酸盐是通过carbonyllithium延伸的N_2形成的。甲硅烷基作用为酮苯基试剂。发现甲硅烷基酸盐与碳电力液（如氧雷亚和苯甲酸乙酸酯）反应，在存在等效量的ME_3AL的情况下。用环己烯氧化物用环己烯的酮烯基通过环酮酮基化的酮苯基处理，然后进行分子内环化，从而产生了乳酸。这些反应是第一个例子，表明甲硅烷基被碳电力捕获。