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在水性条件下合成罗塔xane Cu(I) 三化物
Joby Winn1, Aleksandra Pinczewska, Stephen M Goldup
1School of Biological Sciences, Queen Mary University of London , Joseph Priestly Building, Mile End Road, London E1 4NS, U.K.
Journal of the American Chemical Society
|August 27, 2013
概括
研究人员通过机械结合分离出一种稳定,中性铜 ((I) 三化物中间体. 这种机械互锁的分子被保护免受降解,使得对催化中的反应中间体的新研究成为可能.
科学领域:
- 有机金属化学 有机金属化学
- 超分子化学 超分子化学
- 催化剂是一种催化剂.
背景情况:
- 铜 (I) 催化亚酸循环添加 (CuAAC) 是一个重要的点击化学反应.
- 催化循环中的反应性中间体通常寿命短,难以分离.
- 机械互锁的分子提供了独特的固态环境.
研究的目的:
- 描述一个稳定,中性,单体机械互锁的Cu (I) 三化物的分离.
- 为了研究这种中间体在水条件下的稳定性.
- 探索机械结合在稳定反应性物种中的作用.
主要方法:
- 一个机械互锁的Cu (I) 三化物的一种偶然的分离.
- 在水的条件下,分离化合物的特性.
- 评估Cu (I) -C键对水分,空气和酸的稳定性.
主要成果:
- 一种稳定,中性,单体机械互锁的Cu ((I) triazolide被成功分离出来.
- 罗塔克桑结构以固态方式保护Cu (I) -C键免受反质子化.
- 隔离的中间体在水,空气甚至碳酸盐的存在下表现出显著的稳定性.
结论:
- 该研究表明,通过机械结合,成功分离了关键的催化中间体.
- 机械互锁的架构可以稳定其他反应性有机金属物种.
- 这项工作突出了机械结合在研究催化中的反应中间体方面的潜力.
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Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

