在Au (i) 乙化物中逐步插入基:核性的影响
Juan Cayuela-Castillo1, Francisco J Fernández-de-Córdova1, Matthew S See2
1Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica, Centro de Innovación en Química Avanzada (ORFEO-CINQA), CSIC and Universidad de Sevilla 41092 Sevilla Spain prios1@us.es.
由N-异环碳 (NHC) 支持的双金属黄金复合物,在与二甲基乙烯基碳酸盐 (DMAD) 进行迁移插入反应中表现出增强的反应性. 这种由第二个黄金碎片驱动的改善核友性,使得形成 enyne 产品的反应条件更温和.
科学领域:
- 有机金属化学 有机金属化学
- 黄金催化剂的使用方法
- 碳烯化学 碳烯化学
背景情况:
- 在稳定金属复合物方面,N-异环碳 (NHC) 连接物至关重要.
- 金 ((I) 复合物是众所周知的各种有机转变的催化剂.
- 乙化物复合物是多功能合成中间体.
研究的目的:
- 调查NHC支持的黄金复合体在迁徙插入反应中的反应性.
- 为了比较双金属和单金属黄金物种的反应性.
- 阐明DMAD插入金-乙化物键的机制.
主要方法:
- 对称的同金属和单金属NHC-金 (I) 复合物的合成.
- 黄金复合物的反应与二甲基乙二碳酸盐 (DMAD).
- 实验研究包括运动分析.
- 计算研究 (DFT) 了解反应机制.
主要成果:
- 双金属NHC-gold (I) 复合物随时与25°C的DMAD反应,形成其他产品.
- 单金属类似物需要更严苛的条件 (多余的DMAD,≥110°C) 进行相同的转化.
- 计算和实验数据表明,双金属物种中的乙化物CC键具有增强的核友性.
- 提出了一个阶段性机制,涉及DMAD和不稳定的Au-C债券的有利相互作用.
结论:
- 第二个黄金碎片的存在显著提高了NHC-gold (I) 乙化物复合物的活性.
- 这种增强的反应性归因于乙化物部分的核性增加.
- 这些发现提供了关于由黄金复合体催化迁徙插入反应的机制的见解.
- 双金属系统的反应性可以扩展到其他基质,如异金属.
更多相关视频
09:54Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
09:11Synthesis of Near-Infrared Emitting Gold Nanoclusters for Biological Applications
Published on: March 22, 2020
相关概念视频
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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.
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.
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 Amines: Alkylation of Ammonia and Amines
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
Amines to Amides: Acylation of Amines
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
