不对称的碳-碳合的或anilines与三酸
Taichi Kano1, Yuki Ohyabu, Susumu Saito
1Contribution from the Graduate School of Engineering, Nagoya University, SORST, Japan.
Journal of the American Chemical Society
|May 9, 2002
概括
这项研究详细介绍了使用奇拉胺和有机金属试剂的醇和氨酸的不对称合. 开发的方法在低温下高选择性高效地产生轴性性聚烯化合物.
科学领域:
- 有机化学 有机化学
- 不对称的合成方法
- 催化剂是一种催化剂.
背景情况:
- 轴性性双化合物是各种领域的关键组成部分.
- 开发高效和选择性的合成方法仍然是一个挑战.
研究的目的:
- 为了研究和氨酸衍生物与三酸的不对称合.
- 开发高效的合成各种轴性性聚烯化合物的方法.
主要方法:
- 使用光学活性氨基 (氨酸,氨酸) 作为性辅助剂.
- 采用结构受限的三级胺,氧化物,以及用于联的分子.
- 适用于化与三酸的化. 化用于化和酸的合.
主要成果:
- 在低温 (-40~-20°C) 时,在烯合中实现了高二选择性和反选择性.
- 建立了磁化作为线合的关键技术.
- 成功合成了具有轴性性的一系列多样化的二,三和多烯化合物.
结论:
- 开发了强大的和选择性的方法来对轴性性聚烯化合物的不对称合成.
- 合成的化合物是金属配体,天然产品和螺旋聚合物的宝贵前体.
相关概念视频
Structures of Carboxylic Acid Derivatives
Structure of Carboxylic Acid Derivatives
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Acid Halides to Amides: Aminolysis
Aminolysis is a nucleophilic acyl substitution reaction, where ammonia or amines act as nucleophiles to give the substitution product. Acid halides react with ammonia, primary amines, and secondary amines to yield primary, secondary, and tertiary amides, respectively.
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
Reactions of Acid Anhydrides
The reactions of acid anhydrides are analogous to the reactions of acid chlorides and proceed via a nucleophilic acyl substitution. They only differ in the identity of the leaving group. During an acid chloride reaction, the leaving group is a chloride ion, and the by-product is hydrochloric acid. However, in an acid anhydride reaction, the leaving group is a carboxylate ion, and the by-product is a carboxylic acid.
Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles
Naming Amides
The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and “ic acid,” respectively, with “amide.” In the following example, the IUPAC name ethanamide is derived from ethanoic acid, and the common name, acetamide, is obtained from acetic acid.
The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and “ic acid,” respectively, with “amide.” In the following example, the IUPAC name ethanamide is derived from ethanoic acid, and the common name, acetamide, is obtained from acetic acid.
Nomenclature of Aryl and Heterocyclic Amines
The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is designated for this skeleton. As shown in Figure 1, the common names of the functionalized anilines involve prefixes ortho-, meta-, and para- to indicate the substitution position. Different functionalized aniline derivatives also have notable trivial names.


