铜催化区域分离不对称的终端基因的功能失调
Simin Wang1, Kexin Chen2, Junbo Niu1
1Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
Angewandte Chemie (International ed. in English)
|June 26, 2024
概括
这项研究引入了一种新的铜催化过程,用于基因的不对称功能丧失. 干选择控制了1,1-或1,2-功能失调是否发生,提供了多功能合成途径.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 终端基是有机合成中的多功能构建块.
- 开发用于选择性功能化的催化方法仍然是一个关键的挑战.
- 在功能失调反应中控制区域选择性和立体选择性对于复杂分子合成至关重要.
研究的目的:
- 开发终端基因的联体受控,铜催化区分异常非对称的功能失调.
- 为了实现 1,1-和1,2-功能失调的途径,使用不同的性连接体.
- 探索这种方法与各种基基质的应用,包括工业相关的基质.
主要方法:
- 铜催化级联反应涉及化和化.
- 使用特定的性素配体, (R) -DTBM-Segphos和 (S,S) -Ph-BPE,以控制区域选择性.
- 作为基质,研究了广泛的和终端基因.
- 进行了机械学研究和密度函数理论 (DFT) 计算.
主要成果:
- 证明了终端基因的联体控制的区域分离异位不对称的功能失调.
- 通过 (R) -DTBM-Segphos.实现了独特的不对称的1,1-非功能化.
- 实现了与 (S,S) -Ph-BPE. 的独家不对称的1,2-非功能化.
- 成功地利用乙和作为1,1-功能失调的原料.
- 在晚期功能化和天然产品合成 (Bruguierol A) 中展示了适用性.
结论:
- 开发的催化系统提供了一种强大而通用的方法,用于终端基因的不对称功能.
- 连接体选择提供了对区域选择性的精确控制 (1,1-对1,2-加法).
- 该协议具有广泛的基质范围,良好的功能组耐受性和温和条件,使其对合成化学具有价值.
- 机械洞察力解释了观察到的区域和立体选择性,有助于未来的催化剂设计.
更多相关视频
相关概念视频
02:24Reduction 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
02:17Reduction 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
02:27Preparation 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
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
17.9K
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.
17.9K
02:34Preparation of Alkynes: Dehydrohalogenation
15.7K
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.
15.7K
02:42Acidity of 1-Alkynes
9.7K
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.
9.7K