A Highly Efficient Method for the Synthesis of Nitrogen-containing Materials Using Umpolung Addition to Electron-Deficient Imines

缺电子亚胺的 Umpolung 加成高效合成含氮材料的方法

• 批准号: 23350040
• 负责人: SHIMIZU Makoto
• 金额: $ 12.31万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23350040/
• 关键词: αーイミノエステル; 極性転換反応; タンデム反応; β,γ-不飽和-α-イミノエステル; α-アシロキシイミノエステル; N,N―ジアルキル化反応; N,N.C―トリアルキル化反応; ファインケミカルズ; β,γ-アルキニル-α-イミノエステル; N-アルキル化反応; ビニロガスアルドール反応; α-アミノ-δ-ラクトン; 3-アミノ2-ピロン; N,N-ジアルキル化反応; 極性転換付加反応; α,β‐不飽和‐α‐アミノラクトン; オキシムスルホナート; イミニウム塩

We have already reported that the N-alkylation reaction of alpha-iminoester proceeds using aluminum reagents to give the N-alkylation products in high yields. In the present project, we investigated highly regioselective N-alkylation of beta,gamma-alkenyl-alpha-iminoesters and subsequent directed vinylogous aldol reaction with in situ generated dienolates. It was also found that the sulfenyl group of the alkene part improved the selectivity of both steps, leading to the formation of 3-amino-2-pyrones by anti-elimination of thiols. Furthermore, on treatment with two different Grignard reagents, alpha-acyloxyimino esters gave the corresponding dialkylation products with different substituents on the nitrogen atom. N,N,C-Trialkylated products with all different substituents were obtained via the oxidation and the nucleophilic addition reaction to the resulting iminium salts.

我们已经报道了用铝试剂进行α -亚胺酯n -烷基化反应，得到了高产率的n -烷基化产物。在本项目中，我们研究了β， γ -烷基- α -亚胺酯的高度区域选择性n -烷基化，以及随后与原位生成的二烯醇酯的定向乙烯醛反应。同时发现，烯烃部分的亚砜基提高了这两个步骤的选择性，通过抗巯基消除生成3-氨基-2-吡咯酮。此外，在两种不同的格氏试剂作用下，α -酰基氧亚胺酯在氮原子上得到了不同取代基的对应的二烷基化产物。通过氧化反应和亲核加成反应，得到了含不同取代基的N，N， c -三烷基化产物。

项目成果

Chemistry of Renieramycins. Part 10. Structure of Renieramycin V, A Novel Renieramycin Marine Natural Product Having a Sterol Ether at C-14 position

雷尼尔霉素的化学。

• DOI: 10.3987/com-11-s
• 发表时间: 2012
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: Naoki Saito;Miho Yoshino;Kornvika Charupant;Khanit Suwanborirux
• 通讯作者: Khanit Suwanborirux

Synthesis of Nitrogen‐Containing Heterocycles Using Conjugate Addition Reactions of Nucleophiles to α,β‐Unsaturated Imines

• DOI: 10.1002/chin.201236212
• 发表时间: 2012-05
• 期刊: ChemInform
• 作者: I. Hachiya;Isao Mizota;M. Shimizu

Integrated reactions using addition to conjugated imines and iminium salts

• DOI: 10.1351/pac-con-12-01-03
• 发表时间: 2012-06
• 期刊: Pure and Applied Chemistry
• 影响因子: 1.8
• 作者: Takafumi Nishi;Isao Mizota;M. Shimizu

Synthesis of α-Amino Ketones and O-Alkyloximes by Titanium Tetrahalide Promoted Ring-opening Reaction of 2-Mono-substitued Azetidine-3-ones and Their O-Alkyloximes

四卤化钛促进2-单取代氮杂环丁烷-3-酮及其O-烷基肟的开环反应合成α-氨基酮和O-烷基肟

• 发表时间: 2012
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: S. Ariga;S. Hata;D. Fukuda;T. Nishi;I. Hachiya;M. Shimizu
• 通讯作者: M. Shimizu

Sulfur-Containing Pyridylazulenes: Synthesis and Chromogenic Behaviors for Heavy Metal Ions

含硫吡啶基薁烯：重金属离子的合成和显色行为

• DOI: 10.3987/com-12-12536
• 发表时间: 2012
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: Wakabayashi;S.
• 通讯作者: S.