终端基的介导的C-C合:二核的形成介导的C-C合:二核的形成介导的维нил复合物
Boris Kosog1, Christos E Kefalidis, Frank W Heinemann
1Department of Chemistry and Pharmacy, Inorganic Chemistry, University of Erlangen-Nuremberg, Erlangen, Germany.
(III) 复合物与基因反应,形成新的 (IV) 乙烯复合物. DFT计算显示,对于这些C-C合反应,双金属机制比单金属途径更受青.
科学领域:
- 有机金属化学 有机金属化学
- 化学 的化学
- 催化剂是一种催化剂.
背景情况:
- 复合物对催化应用具有兴趣.
- (III) 复合物与不和碳化合物显示出反应性.
- 了解反应机制对于开发新的催化过程至关重要.
研究的目的:
- 为了合成和表征新的乙烯复合物.
- 研究 (III) 复合物与基因的反应机制.
- 阐明控制碳化合物碎片协调的因素.
主要方法:
- (III) 和 (IV) 复合物的合成.
- 与终端 bis-alkynes 和 monoalkynes 的 C-C 合反应.
- 由此产生的乙烯复合物的晶体学表征.
- 密度函数理论 (DFT) 计算以建模反应路径.
主要成果:
- 合成了四种新的乙烯复合物,这是第一个以晶体学特征的复合物.
- 与二-基因的反应产生了循环 (IV) 乙烯复合物.
- 与单基因的反应产生了非循环(IV) 乙烯基复合物.
- DFT计算支持对观察到的C-C合反应的双金属机制.
结论:
- 该研究报告了第一个结晶学特征的乙烯复合物.
- 为形成这些复合体,提出了一种双金属机制,并得到了计算支持.
- 这些发现提供了关于复合物与基因的反应性和潜在的催化应用的见解.
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相关概念视频
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Preparation of Alkynes: Alkylation Reaction
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.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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: Dehydrohalogenation
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 to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
