Synthesis of Optically Active Allenecarboxylic Acid Derivatives by Asymmetric Carbonylation Reactions

不对称羰基化反应合成光学活性丙二烯羧酸衍生物

• 批准号: 09650958
• 负责人: IMADA Yasushi
• 金额: $ 2.24万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650958/
• 关键词: Carbon Monoxide; Carbonylation Reactions; Palladium Catalysts; Optically Active Phosphines; Kinetic Optical Resolutions; Allenylpalladium Complexes; Propargylic Esters; Oprically Active Allenes; 速度論的光学分割; 光学活性アレン化合物; π-アリルパラジウム錯体; 一酸化酸素; π-アリル

I have been studied carbonylation reactions of allylic and propargylic compounds. In this project, I studied asymmetric version of these carbonylation reactions to accomplish asymmetric carbon-carbon bond formation using carbon monoxide.1. Carbonylation of allylic phosphates in the presence of a palladium complex catalyst bearing an optically active monodentate phosphine ligand proceeds smoothly to give optically active β, γ-unsaturated carboxlic acid esters. This is the first example of asymmetric version of allylic carbonylation reactions.2. Optically active propargylic phosphates are carbonylated in the presence of a palladium complex catalyst with inversion of configuration to give axially chiral allenecarboxylic acid esters without loss of optical purity.3. Carbonylation of racemic propargylic phosphates using a palladium complex catalyst bearing an optically active bidentate phosphine ligand proceeds with kinetic optical resolution to give axially chiral allenecarboxylic acid esters along with recovered optically active propargylic phosphates. This is the first example of asymmetric synthesis of allene compounds using a catalytic amount of chiral compound.

我研究了烯丙基和炔丙基化合物的羰基化反应，在这个项目中，我研究了这些羰基化反应的不对称形式，以使用一氧化碳实现不对称碳-碳键的形成。1。带有光学活性的单齿膦配体可以顺利地生成活性的β，γ-不饱和羧酸酯，这是不对称形式的第一个例子。烯丙基羰基化反应。 2. 在钯络合物催化剂存在下，通过构型反转，将旋光丙炔磷酸酯羰基化，得到轴向手性丙二烯羧酸酯，而不会损失光学纯度。 3. 使用钯络合物催化剂轴承进行外消旋丙炔磷酸酯的羰基化。光学活性二齿膦配体通过动力学光学拆分得到轴向手性丙二烯羧酸这是使用催化量的手性化合物不对称合成丙二烯化合物的第一个例子。

项目成果

Hiroaki Ohtake: "Regioselective Synthesis of Nitrones by Decarboxylative Oxidation of N-Alkyl-α-Amino Acids and Application to the Synthesis of 1-Azabicyclic Alkaloids"Bull. Chem. Soc. Jpn.. 72. 2737-2754 (1999)

Hiroaki Ohtake：“N-烷基-α-氨基酸的脱羧氧化合成硝酮及其在 1-氮杂双环生物碱合成中的应用”Soc. 72. 2737-2754 (1999)

Shun-Ichi Murahashi: "Synthesis of Homochiral β-Sulfinyl Nitrones and Their Application for Enantioselective Synthesis of (+)-Euphococcinine"Heterocycles. 52. 557-561 (2000)

Shun-Ichi Murahashi：“同手性 β-亚磺酰硝酮的合成及其在 (+)-Euphococcinine 的对映选择性合成中的应用”杂环。 52. 557-561 (2000)

Toru Kawakami: "Asymmetric Synthesis of β-Amino Acids by Addition of Chiral Enolates to N-Acyloxyiminium Ions and Application for Synthesis of Optically Active…"Organic Letters. 1. 107-110 (1999)

Toru Kawakami：“通过向 N-酰氧基亚胺离子添加手性烯醇化物来不对称合成 β-氨基酸以及用于合成光学活性…”有机快报。

Shun-ichi Murahashi: "Transition Metals for Organic Synthesis"VCH, Weinheim. 378-383 (1998)

Shun-ichi Murahashi：“用于有机合成的过渡金属”VCH，Weinheim。

Toru Kawakami: "Reversal of Diastereoselectivity of the Reaction of Chiral Boron and Titanium Enolates with Nitrones via N-Acyloxyiminium Intermediates. Asymmetric Synthesis of Diastereomeric"Chem. Lett.. 795-796 (1999)

Toru Kawakami：“手性硼和钛烯醇化物与硝酮通过 N-酰氧基亚胺中间体反应的非对映选择性的逆转。非对映异构体的不对称合成”Chem。