The Production of Chiral beta-Aminoalcohols to be excellent catalysts for the synthesis of optically active sec-alcohols.

手性β-氨基醇的生产是合成光学活性仲醇的优异催化剂。

• 批准号: 03559005
• 负责人: OGUNI Nobuki
• 金额: $ 4.03万
• 依托单位: YAMAGUCHI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03559005/
• 关键词: optically active beta-aminoalcohols; asymmetric reaction; optical resolution; asymmetric alkylation of aldehydes; 光学活性β-アミノアルコ-ル; 不斉アルキル化反応; 酒石酸ジイソプロピル; チタニウム化合物; 光学分割

The synthetic methods of optically active sec-alcohols are knwon that asymmetric reductions of unsymmetrical ketones or the asymmetric alkylation of aldehydes are useful methods. The author found the asymmetric alkylation method of aldehydes with dialkylzinc catalyzed by beta-aminoalcohols in 1983. For the first time we studied the synthetic method of optically active 2-hydroxy-3,3-dimethyl-butylamine which was excellent catalysts for alkylation of aldehydes. High yield production ofmonobromination or monochlorination of pinacolone was succeeded by the reaction at 0ﾟC.The reduction of monohalogeno-pinacolone was performed by NaBH_4 in MeOH-H_2O,followed by treatment of alkalline to give t-butylethylene oxide. Thus, obtained t-butylethylene oxide was reacted with N-magnesium salt of sec-amines to give N-dialkyl-2-hydroxy-3,3-dimethyl-1-butylamines in high yield. By this method a variety of beta-aminoalcohols could be prepared.Rac-beta-aminoalcohols was resolved by Sharpless asymmetric oxidation which was very useful method for resolving beta-aminoalcohols. The production of optically active beta-amino-alcohols in industrial scale is now in pending, because the demand of the products is now in step of researching.

已知旋光仲醇的合成方法，不对称酮的不对称还原或醛的不对称烷基化是有用的方法。作者于1983年发现了β-氨基醇催化的二烷基锌醛不对称烷基化方法，并首次研究了光学活性2-羟基-3,3-二甲基丁胺的合成方法，该胺是醛类烷基化的优良催化剂。在0℃下反应成功高产率地生产了频哪酮的单溴化或单氯化。在MeOH-H_2O中用NaBH_4还原一卤代频哪酮，然后用碱处理得到叔丁基环氧乙烷。由此，获得的叔丁基环氧乙烷与仲胺的N-镁盐反应，以高收率得到N-二烷基-2-羟基-3，3-二甲基-1-丁胺。通过该方法可以制备多种β-氨基醇。利用Sharpless不对称氧化法拆分Rac-β-氨基醇是一种非常有用的拆分β-氨基醇的方法。光学活性β-氨基醇的工业规模生产目前尚待进行，因为该产品的需求正在研究中。

项目成果

M.Hayashi,Y.Miyamoto,T.Inoue,N.Oguni: "Enantioselective Trimethylsilylcyanation of some aldehyde catalyzed by chiral Sciff base-titanium alkoxide complex." Journal of Organic Chemistry. 58. (1993)

M.Hayashi、Y.Miyamoto、T.Inoue、N.Oguni：“手性 Sciff 碱-钛醇盐络合物催化某些醛的对映选择性三甲基甲硅烷基化。”

M.Hayashe,T.Inoue,N.Oguni: "Novel Enantioselective Reaction of Diketene with Some Aldehydes Promoted by Chiral Schiff Base-Titanium Alkoxide Complex." Journal Chemical Society,Chemical Communications. 341-342 (1994)

M.Hayashe、T.Inoue、N.Oguni：“手性希夫碱-钛醇盐复合物促进双烯酮与某些醛的新型对映选择性反应”。

M.Hayashi,Y.Miyamoto T.Inoue,N.Oguni: "Enantioselective Trimethylsilylcyanation of some aldehyde catalyzed by chiral Sciff base-titanium alkoxide complex." Journal of Organic Chemistry. 58. 1515-1522 (1993)

M.Hayashi、Y.Miyamoto T.Inoue、N.Oguni：“手性 Sciff 碱-钛醇盐络合物催化某些醛的对映选择性三甲基硅烷氰化。”

M.Hayashi,T.Kaneko,N.Oguni: "An efficient preparation of optically active allylic alcohols,2-furyl alcohols,and 2-thienyl alcohols by catalytic asymmetric alkylation." Journal of Chemical Society,Perkin Trans,I. 25-28 (1991)

M.Hayashi、T.Kaneko、N.Oguni：“通过催化不对称烷基化有效制备光学活性烯丙醇、2-呋喃醇和 2-噻吩醇。”

M.Hayashi,H.Miwata,N.Oguni: "Kinetic resolution of racemic aldehydes by enantioselective alkylation" J.Chem.Soc.Perkin Trans I. 1167-1171 (1991)

M.Hayashi、H.Miwata、N.Oguni：“通过对映选择性烷基化动力学拆分外消旋醛” J.Chem.Soc.Perkin Trans I. 1167-1171 (1991)