和二烯的分子间基催化化与初级素的化
Michael B Ghebreab1, Christine A Bange, Rory Waterman
1Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.
Journal of the American Chemical Society
|June 18, 2014
概括
一种新型的复合物在温和条件下利用初级素催化和二烯的抗马尔科夫尼科夫化. 这种反应为二级或三级素产品提供了选择性的途径,对进一步的合成应用有价值.
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:
- 化是形成碳键的关键反应.
- 开发高效的催化系统用于化仍然是一个活跃的研究领域.
- 初级素是多用途的构建块,但选择性地功能化可能具有挑战性.
研究的目的:
- 开发一种温和高效的催化系统,用于终端和二烯的化.
- 调查催化系统对二级和三级素产品的选择性.
- 为了证明由此产生的素产品的合成效用.
主要方法:
- 作为催化剂使用了一种特定的复合物,[κ(5)-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr (1),作为催化剂.
- 作为源使用初级素 (RPH2; R = Cy, Ph).
- 在温和条件下与终端和二烯进行反应.
主要成果:
- 实现了对和二烯的初级素的独家反马尔科夫尼科夫添加.
- 根据反应条件证明了二级或三级素产物的选择性形成.
- 在随后的催化非对称化中展示了二次素产物的实用性.
结论:
- 开发的催化化提供了一种温和而有选择的路径,以功能化素.
- 催化系统可以控制化程度 (二级与三级产品).
- 合成的素产物作为进一步合成转化,包括不对称催化剂的有价值的中间体.
相关概念视频
Electrophilic Addition to Alkynes: Hydrohalogenation
9.3K
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
9.3K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
19.7K
Introduction
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.
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.
19.7K
Hydroboration-Oxidation of Alkenes
9.9K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
9.9K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
6.8K
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.
6.8K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.0K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.0K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.9K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.9K


