选择性C-H激活α到初级氨基. 在催化性,分子内α-化过程中,桥梁金属阿齐里丁具有催化性,分子内α-化作用
Jason A Bexrud1, Patrick Eisenberger, David C Leitch
1Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, B.C, Canada, V6T 1Z1.
Journal of the American Chemical Society
|January 29, 2009
概括
研究人员开发了一种新的催化方法,用于使用桥梁金属阿齐里丁复合物对原始氨基的α-化. 这种方法有效地创建了四级性中心,而不需要保护组.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 合成有机化学 合成有机化学
背景情况:
- 选择性C-H激活对于高效的合成至关重要.
- 开发用于氨基功能化的新催化系统是一个持续的挑战.
- 与相邻的四次性性中心是重要的结构动图.
研究的目的:
- 开发一种用于原始氨基的α-化新型催化方法.
- 合成和描述第一个桥梁金属阿齐里丁复合物.
- 探索四元性性中心的形成,从α到.
主要方法:
- 选择性的α-C-H激活反应.
- 开发新的二二酸盐复合物.
- 使用初步研究进行机制研究.
主要成果:
- 首个桥梁金属阿齐里丁复合物的成功合成.
- 在没有保护的情况下实现的初级氨基的催化α-化.
- 已经证明了四级性中心的形成,从α到.
- 将桥梁金属阿齐里丁作为活性中间体的鉴定.
结论:
- 开发的方法为初级胺基的α-化提供了一条新的途径.
- 二二酸复合物是这种转变的有效催化剂.
- 反应使得复杂的分子架构的构建成为可能.
相关概念视频
Preparation of Amines: Alkylation of Ammonia and Amines
Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines along with a quaternary ammonium salt through successive SN2 reactions. This process of making the quaternary salt through the direct alkylation method is called exhaustive alkylation.
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Preparation of 1° Amines: Gabriel Synthesis
Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
α-Alkylation of Ketones via Enolate Ions
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the strong interaction...


