通过加的基脱来获得Z-Enynes
Alexandra K Bodnar1, Timothy R Newhouse1
1Department of Chemistry, Yale University, 225 Prospect St, New Haven, Connecticut, 06520-8107, United States.
Angewandte Chemie (International ed. in English)
|April 9, 2024
概括
研究人员开发了一种新的Z选择性脱方法,用于从基中产生1,3-基. 这种催化氧化系统克服了合成Z-基的挑战,提供了一条新的合成途径.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 基是有机合成中的关键组成部分.
- 由于热力学偏好E-基因,Z-基因在合成上很难获得.
- 选择性Z-基合成方法是有限的.
研究的目的:
- 报告一种新的Z选择性脱方法.
- 为了从类化合物中合成1,3-类.
- 为了研究Z-烯形成的机制.
主要方法:
- 用催化氧化系统.
- 的脱. 的脱. 的脱.
- 动态同位素效应 (KIE) 研究.
- 同体化实验. 同体化实验.
主要成果:
- 实现了1,3-enynes的Z选择性合成.
- 通过KIE. 确定了propargylic位置的deprotonation作为速度限制步骤.
- 确认的Z-选择性是通过异构化研究的动力效应.
结论:
- 开发了一种新的共催化Z-选择性propargylic脱.
- 提供了对Z-烯形成的立体选择机制的见解.
- 建立了一条新的途径来获取有价值的1,3-enyne化合物.
更多相关视频
相关概念视频
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.7K
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.
7.7K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.3K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.3K
Preparation of Alkynes: Alkylation Reaction
10.1K
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.
10.1K
Preparation of Alkynes: Dehydrohalogenation
15.8K
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.
15.8K
Reduction of Alkenes: Catalytic Hydrogenation
12.0K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
12.0K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.0K
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.
18.0K


