Development of Highly Stereoselective Carbon-Carbon Bond Forming Reactions

高立体选择性碳-碳键形成反应的进展

• 批准号: 63470018
• 负责人: MUKAIYAMA T.
• 金额: $ 5.63万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470018/
• 关键词: chiral diamine; tin(II) enolate; aldol reaction; Michael reaction; 1,2-cis Ribofuranoside; tin(II) triflate; diphosphonium salt; Prins-type reaction; 1、2ーシスリボフラノシド; トリメチルシリルシアニド; シリルエノ-ルエ-テル; 2価スズのエノラート; キラルなジアミン; エナンチオ選択的マイケル反応; 不斉触媒; 塩化トリ

New synthetic methods for highly stereoselective carbon-carbon bond formations have been developed.1. In the presence of trimethylsilyltriflate, chiral diamine coordinated tin(II) enolates react with alpha,beta-unsaturated ketones to afford the corresponding Michael adducts in good ees. This reaction is applied to the catalytic asymmetric Michael reaction of tin(II) enethiolates with alpha,beta-unsaturated ketones.2. Acetals smoothly react with activated or simple 1,1-di-substituted olefins to give the corresponding adducts in the coexistence of catalytic amounts of trimethylsilyl chloride (trityl-chloride) and tin(II) chloride with a stoichiometric amount of lithium perchlorate. Aldehydes also react with the olefins to form the Prins-type reaction products by further addition of alkoxy trimethylsilane to the above catalyst system.3.1,2-cis-Ribofuranosides are stereoselectively prepared in high yields by the reaction of 1-0-acetyl-beta-D-ribose with silylated nucleophiles by the promotion of a new catalyst system, the combined use of a catalytic amount of tin(IV) chloride and tin(II) triflate with a stoichiometric amount of lithium perchlorate.4. In the presence of a catalytic amount of diphosphonium salt, aldol reaction of silyl enol ethers with aldehydes or acetals and the Michael reaction of silyl enol ethers with alpha,beta-unsaturated ketones or acetals smoothly proceed to produce the corresponding adducts in fairly good yields. Imines also react with ketene silyl acetals to give the corresponding beta-aminoesters in good yields in the presence of the above catalyst.5. In the presence of a catalytic amount of (Rh(COD)Cl)_2, trimethyl cyanide reacts with acetals derived from aliphatic, unsaturated or aromatic aldehydes to form the corresponding alpha-cyano derivatives of [Rh(COD)Cl]_2 and trimethylsilyl cyanide, silyl enol ethers also react with acetals to yield the corresponding aldol adducts under almost neutral conditions.

已经开发了高度立体碳碳键形成的新合成方法。1。在三甲基甲硅烷基三叶酸酯的存在下，手性二胺配位锡（II）与α型β-饱和酮的反应相应，可为良好的EES提供相应的迈克尔加合物。该反应应用于锡（II）乙醇酸盐与α，β-含β-不饱和酮的催化不对称迈克尔反应。2。 acetals与活化或简单的1,1-Di取代的烯烃平滑反应，从而在催化量的三甲基甲硅烷基氯化物（三甲基氯化物）和氯化锡（II）氯化物的共存中与相应的加合物形成了相应的加合物。 Aldehydes also react with the olefins to form the Prins-type reaction products by further addition of alkoxy trimethylsilane to the above catalyst system.3.1,2-cis-Ribofuranosides are stereoselectively prepared in high yields by the reaction of 1-0-acetyl-beta-D-ribose with silylated nucleophiles by the promotion of a new catalyst system, the combined use of a用化学计量量的高氯酸锂催化量的锡（IV）氯化物和锡（II）（II）。4。在存在催化量的二磷酸盐的情况下，甲硅烷基烯醇醚与醛或乙烯的醛醇反应，以及Silyl烯醇乙醇与α-不饱和酮或乙烯的迈克尔反应，以相当良好的良好产量产生相应的加入。在上述催化剂存在下5。 In the presence of a catalytic amount of (Rh(COD)Cl)_2, trimethyl cyanide reacts with acetals derived from aliphatic, unsaturated or aromatic aldehydes to form the corresponding alpha-cyano derivatives of [Rh(COD)Cl]_2 and trimethylsilyl cyanide, silyl enol ethers also react with acetals to yield the corresponding aldol adducts under almost中性条件。

项目成果

T.Mukaiyama: "The Addition Reaction of Acetals to Activated Olefins under Extremely Mild Conditions" Chemistry Letters. 1988. 1101-1104 (1988)

T.Mukaiyama：“极温和条件下乙缩醛与活化烯烃的加成反应”化学快报。

T.Mukaiyama: "〔1,2-Benzenediolate(2-)-O,O'〕oxotitanium.A Mild and Efficient Catalyst for the Michael Reaction of Ketene Silyl Acetals with α,β-Unsaturated Ketones" Chemistry Letters. 1989. 1171-1174 (1989)

T.Mukaiyama：“[1,2-苯二醇(2-)-O,O]氧钛。烯酮甲硅烷基缩醛与 α,β-不饱和酮发生迈克尔反应的温和高效催化剂”，化学快报，1989 年。 -1174 (1989)

T.MUKAIYAMA.: Chemistry Letters. 1988. 1291-1294 (1988)

T.MUKAIYAMA.：化学快报。

T.Mukaiyama: "Efficientl Activation of Acetals towaerd Nucleophiles with 〔Rh(COD)Cl〕_2 Catalyst.New Method for the Preparation of Aldols from Acetals and Silyl Enol Ethers by the Combined Use of Catalytic Amounts of 〔Rh(COD)Cl〕_2 and Trimethtl-silyl Cyani

T.Mukaiyama：“用〔Rh(COD)Cl〕_2催化剂有效活化缩醛对亲核试剂。联合使用催化量的〔Rh(COD)Cl〕由缩醛和硅烯醇醚制备羟醛的新方法_2和三甲基甲硅烷基氰基

T. Mukaiyama: "Stereoselective 1,2-cis Glycosylation Reaction of 1-O-Acetylribose with Silylated Nucleophiles by the Promotion of a New Catalyst System" Chemistry Letters, 1989, 145 - 148.

T. Mukaiyama：“通过新催化剂系统的促进，1-O-乙酰核糖与硅烷化亲核试剂的立体选择性 1,2-顺式糖基化反应”，《化学快报》，1989 年，145 - 148。