Development of Highly Stereoselective Reaction in Metal and Hetero-Atom Combined Reaction Filed

金属与杂原子联合反应领域高立体选择性反应的研究进展

• 批准号: 04453098
• 负责人: UTIMOTO Kiitiro
• 金额: $ 4.54万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453098/
• 关键词: Lanthonoids Reagent; Diastereoselectivity; Optically Active Amine; 1,4-Addition; beta-Keto Amide; Organomanganese Reagent; β-ケトアミド; 有機マンガン反応剤; 1,4付加; 光学活性アルコール; オキサチアン化合物; βーケトアミド; カルシウム反応剤

(1) An addition of various organolithium compounds to imine or hydrazine derived from optically active 2-formy1-1,3-oxathiane gave amine derivatives with high diastereoselectivity (>99% de) in good yields.(2) Diastereoselective 1,4-addition reaction of optically active 2-butenoy1-1,3-oxathiane was studied. The addition of organocupper reagent in the presence of YbCl_3 provided 1,4-adduct as a single diastercomeric compound. On the other hand, treatment with organomagnesium reagent in the presence of a catalytic amount of CuBr gave the other diastereomer with high diastereoselectivity.(3) Lanthanoid triflate proved to be a good catalyst for the 1,4-addition reaction of various amines to alpha, beta-unsaturated esters. The reaction was succesfully applied to a diastereoselective synthesis of optically active beta-lactams.(4) Stereoselective alkylation of 2-alky1-2-formylamide with alky1-aluminium dichloride was achieved. An addition of trialkylaluminium or alkylmanganese chloride to 2-methy1-3-oxo-amide gave the corresponding 3-hydroxy-2-methylamide with high stereoselectivity.

(1)将各种有机锂化合物与光学活性的2-甲酰基-1，3-氧硫杂环己烷衍生的亚胺或肼加成，得到了高非对映选择性的胺衍生物（de>99%），产率良好。(2)研究了光学活性2-丁烯酰基-1，3-氧硫杂环己烷的非对映选择性1，4-加成反应。在YbCl_3存在下，加入有机铜试剂，得到1，4-加成物。另一方面，在催化量的CuBr存在下用有机镁试剂处理，得到具有高非对映选择性的另一种非对映体。(3)三氟甲磺酸镧系元素被证明是各种胺与α，β-不饱和酯的1，4-加成反应的良好催化剂。该反应成功地应用于光学活性β-内酰胺的非对映选择性合成。(4)用烷基二氯化铝对2-烷基-2-甲酰胺进行了立体选择性烷基化反应。三烷基铝或烷基锰的氯化物与2-甲基-3-氧代酰胺的加成反应，得到了高立体选择性的3-羟基-2-甲基酰胺。

项目成果

Seijiro MATSUBARA: "Diastereoselective Addtion of Organometallic Reagents to Imines or Hydrazones Containing 1,3-Oxathiane As a Chiral Template" Chemistry Letters. (印刷中). (1994)

Seijiro MATSUBARA：“将有机金属试剂非对映选择性添加到含有 1,3-氧杂硫烷的亚胺或腙作为手性模板”（化学快报）（1994 年出版）。

Toshiaki YOKOO: "Ytterbium Catalyzed Oxidation of Alcohols tp Aldehydes and Ketones by Means of Iodoaldejydes" Chemistry Letters. 571-572 (1993)

Toshiaki YOKOO：“镱通过碘醛催化醇类和酮类的氧化”化学快报。

Toshiaki YOKOO: "Ytterbium Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Means of Iodosylbenzene" Chemistry Letters. 571-572 (1993)

Toshiaki YOKOO：“镱通过碘酰苯催化醇氧化成醛和酮”化学快报。

Seijiro MATSUBARA: "Lanthanoid Triflate Catalyzed Conjugate Addition of Amines to α,β-Unsaturated Esters.A Facile Route to Optically Active β-Lactum" Chemistry Letters. (印刷中). (1994)

Seijiro MATSUBARA：“镧系三氟甲磺酸盐催化胺与 α,β-不饱和酯的共轭加成。制备光学活性 β-内酯的简便途径”（正在出版）。

Masahiko TANIGUCHI: "Stereoselective Reduction of 2-Methyl-3-oxo Esters(or Amides)with Sodium Borohydride Catalyzed by Magnesium Choride or Tetrabutylammonium Borohydride.A Practical Preparation of erythro and threo-3-Hydroxy-2-methyl Esters(or Amides)" T

Masahiko TANIGUCHI：“氯化镁或硼氢化四丁基铵催化的硼氢化钠立体选择性还原 2-甲基-3-氧代酯（或酰胺）。赤式和苏式-3-羟基-2-甲基酯（或酰胺）的实际制备