シンコナアルカロイド/スルフィニル塩化物の組み合わせ:アルコールのエナンチオセレクティブスルフィニル化剤
Norio Shibata1, Mitsuharu Matsunaga, Masaya Nakagawa
1Department of Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan. nozshiba@nitech.ac.jp
Journal of the American Chemical Society
|February 3, 2005
まとめ
研究者らは,シンコナアルカロイドとスルフィニル塩化物を用いた非対称的なスルフィニレーションのための新しい方法を開発しました. この画期的な技術は,アルネスルフィナートの両方のエナントオメールを高純度で効率的に生成します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- アシンメトリック・シンセシス
背景:
- サルフィニレーション反応は,キラル硫黄化合物の合成に不可欠である.
- サルフィニレーションのための効率的な非対称的な方法の開発は,依然として課題です.
研究 の 目的:
- 新規の非対称スルフィニレーション法を導入する.
- シンコナアルカロイド/スルフィニル塩化物系をアキラルアルコールの非対称スルフィニル化剤として利用する.
主な方法:
- シンコナ・アルカロイドとスルフィニル塩化物の組み合わせを使用しています.
- 開発された反応剤システムでアキラルアルコールを反応させる.
主要な成果:
- アキラルアルコールの最初の非対称的なスルフィニル化に成功した.
- アレネスルフィナートの2つのエナティオメールを,高いエナティオメール過量 (最大99% ee) で得られた.
結論:
- 開発された方法は,キラルアルネスルフィネートへの新しい効果的な経路を提供します.
- 高いエナチオセレクティビティは,ダイナミックな運動解像度メカニズムが関与している可能性があることを示唆しています.
関連する概念動画
Formation of Complex Ions
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
Coordination Compounds and Nomenclature
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
Metal-Ligand Bonds
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Nitriles to Ketones: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
The mechanism begins with a nucleophilic attack by the Grignard reagent...
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Masking and Demasking Agents
EDTA titrations may necessitate masking and demasking agents to temporarily protect a particular metal ion in a mixture from the EDTA reaction. These agents facilitate the sequential analysis of the metal ions by forming stable complexes with some—but not all—metal ions during certain steps.
There are many masking agents, such as cyanide, fluoride, triethanolamine, thiourea, and 2,3-bis(sulfanyl)propan-1-ol (formerly 2,3-dimercapto-1-propanol), with the masking agent chosen based on the metal...
There are many masking agents, such as cyanide, fluoride, triethanolamine, thiourea, and 2,3-bis(sulfanyl)propan-1-ol (formerly 2,3-dimercapto-1-propanol), with the masking agent chosen based on the metal...


