易斯基/铜合作催化非对称的α-氨基化与迪亚齐里丁
Jin Song1, Zi-Jing Zhang1, Shu-Sen Chen1
1Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemistry, and Center for Excellence in Molecular Synthesis of CAS , University of Science and Technology of China , Hefei 230026 , China.
Journal of the American Chemical Society
|January 30, 2018
概括
一种新的合作催化方法使得的抗选择性α-氨基化成为可能. 这一策略产生了性乙烯酸和铜中间体,产生了具有优异的立体化学控制的高度丰富的素.
科学领域:
- 有机化学
- 催化剂
- 不对称的合成
背景情况:
- 对于药物而言,选择性合成至关重要.
- 开发高效的化方法以实现的α功能化仍然是一个挑战.
研究的目的:
- 开发一种新型的胺酶.
- 在合成水素中实现高立体化学控制.
主要方法:
- 采用了易斯基/铜合作催化策略.
- 从五二乙烯中生成过渡性C1-氨基乙烯酸.
- N,N-di-t-butyldiaziridinone和Cu (I) 形成了一个铜中间体.
主要成果:
- 合作催化允许高水平的立体化学控制.
- 一组多样化的素合成了良好的产量.
- 获得了优异的抗选择性 (90- 99% ee).
结论:
- 开发的方法提供了一条有效的途径,以获得丰富的素.
- 合作催化提供了一种强大的非对称合成策略.
相关概念视频
Lewis Acids and Bases
48.5K
In 1923, G. N. Lewis proposed a generalized definition of acid-base behavior in which acids and bases are identified by their ability to accept or to donate a pair of electrons and form a coordinate covalent bond.
A coordinate covalent bond (or dative bond) occurs when one of the atoms in the bond provides both bonding electrons. For example, a coordinate covalent bond occurs when a water molecule combines with a hydrogen ion to form a hydronium ion. A coordinate covalent bond also results when...
A coordinate covalent bond (or dative bond) occurs when one of the atoms in the bond provides both bonding electrons. For example, a coordinate covalent bond occurs when a water molecule combines with a hydrogen ion to form a hydronium ion. A coordinate covalent bond also results when...
48.5K
Lewis Acids and Bases
17.6K
This lesson delves into Lewis acids and bases in the context of the octet rule for electron-deficient compounds. Here, the concept is discussed, emphasizing the group 13 elements like boron or aluminium. Since group 13 elements possess three valence electrons, they form trivalent compounds with a sextet of electrons and a vacant orbital for the central atom. Consequently, these electron-deficient compounds accept electrons from other species to complete their octet in a chemical reaction. They...
17.6K
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
4.2K
Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in a reversible manner, forming carboxylic acids and alcohols.
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
4.2K
Cooperative Allosteric Transitions
8.9K
Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
8.9K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
5.0K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
5.0K
Lewis Symbols and the Octet Rule
82.6K
Chemical bonds are complex interactions between two or more atoms or ions, which reduce the potential energy of the molecule. Gilbert N. Lewis developed a model called the Lewis model that simplified the depiction of chemical bond formation and provided straightforward explanations for the chemical bonds seen in most common compounds.
82.6K


![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)