动态动态分辨率的2 - - - - - - 甲:亚热选择性 - 催化转移化合
José A Carmona1, Patricia Rodríguez-Salamanca1, Rosario Fernández2
1Instituto Investigaciones Químicas (CSIC-US) and Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/Américo Vespucio 49, 41092, Sevilla, Spain.
这项研究引入了催化动态动力学分辨率,用于从化物中制造性分子. 该方法通过在化过程中同时形成中央和轴向性来实现高选择性.
科学领域:
- 有机化学 有机化学
- 不对称的催化剂.
- 有机金属化学 有机金属化学
背景情况:
- 动态动力学分辨率 (DKR) 对于合成体纯化合物至关重要.
- 在有机合成中,开发用于安装轴性奇拉性的人体选择方法仍然是一个重大挑战.
- 催化为不对称转换提供了独特的反应性.
研究的目的:
- 开发一种新型的以为催化剂的二---8-) 甲和1-甲的新型体育选择性动态动态分辨率 (DKR).
- 为了在单一的催化步骤中实现同时安装中央和轴向性.
- 在这个DKR过程中探索种族化和结合的机制.
主要方法:
- 采用一个正轨环金属化-DM-BINAP复合物作为催化剂.
- 使用转移化合与酸作为化试剂.
- 调查基质范围并优化反应条件以获得高立体选择性.
主要成果:
- 实现了高的二选择性和优秀的反体过量在2 - - - - - - - - - - - - - - - - - - - - - - - - - - - 基诺林-8-) 甲和1 - - - - - - - - - 纳甲的结合.
- 证明了中央和轴性性同时形成.
- 鉴定了一种暂时的易斯酸相互作用机制,用于基质的种族化.
结论:
- 开发的Ir-催化DKR提供了一条高效的途径,以获得具有中枢和轴向性,具有高度性丰富的分子.
- 在这种转化过程中,正轨循环金属化-DM-BINAP催化剂非常有效.
- 对基质种族化的机械洞察力为DKR过程提供了更深入的理解.
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
06:46Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
相关概念视频
Nucleophilic Aromatic Substitution: Elimination–Addition
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
α-Alkylation of Ketones via Enolate Ions
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
