1-alkoxyallene作为区域和立体控制的合反应的有效前体,通过 bis-stannylation 通过阿里法性化物进行合反应
David R Williams1, Micheal W Fultz
1Department of Chemistry, Indiana University, Bloomington, Indiana 47405-7102, USA. williamd@indiana.edu
Journal of the American Chemical Society
|October 20, 2005
概括
一种新的 bis-stannane 试剂由 1- ((methoxy) methoxyallene 合成,用于立体选择性结合反应. 这种试剂有效地产生1,2-二醇衍生物,使得复杂的立体三与差异化氧取代剂.
科学领域:
- 有机化学 有机化学
- 有机金属化学 有机金属化学
- 合成化学 合成化学
背景情况:
- 艾伦的功能化对于合成复杂的有机分子至关重要.
- 有机蛋白化合物在碳-碳键形成中具有独特的反应性.
- 聚氧化化合物的立体选择性合成仍然是一个挑战.
研究的目的:
- 开发一种用于立体选择性合并的新 bis-stannane 试剂.
- 为了探索合成的试剂与各种甲基的反应性.
- 为了研究用差异化氧取代剂构建立体三元体的结构.
主要方法:
- 1 - - 甲基甲基烯的双化,以产生化试剂.
- 比斯斯坦与化物的立体选择性反应.
- 使用NMR光谱和X射线衍射分析反应产物的分析.
主要成果:
- 双化成功生成了一个高度反应的化试剂.
- 与合物的立体选择性反应提供了1,2-二醇衍生物的良好产量.
- 对alpha-alkoxyaldehydes进行化控制的添加有效地构建了3,4-anti-4,5-syn-stereotriads.
结论:
- 开发的 bis-stannane 是一种用于立体选择性合并的有效试剂.
- 该方法允许高效合成具有多个氧气功能的复杂立体三元体.
- 这项工作为在有机合成中构建复杂的分子架构提供了有价值的工具.
相关概念视频
Introduction to Electrophilic Addition Reactions of Alkenes
The double bond in a simple, unconjugated alkene is a region of high electron density that can act as a weak base or a nucleophile. The filled π orbital (HOMO) of the double bond can interact with the empty LUMO of an electrophile. A bonding interaction occurs when the electrophile attacks between the two carbons; the electrophile then accepts a pair of electrons from the π bond and undergoes addition across the double bond, yielding a single product.
Addition and elimination reactions can be...
Addition and elimination reactions can be...
Halogenation of Alkenes
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion 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 Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
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.
Radical Substitution: Allylic Bromination
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...


