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Metathetic approach to new NORPHOS-related bisphosphanes: facile synthesis and application in asymmetric hydrogenation
Pure and Applied Chemistry ( IF 1.8 ) Pub Date : 2021-04-01 , DOI: 10.1515/pac-2020-1205
Katarzyna Szwaczko 1 , Barbara Miroslaw 1 , Oleg M. Demchuk 2, 3 , Grzegorz Wójciuk 1 , Liliana Mazur 1 , Kazimierz Michał Pietrusiewicz 1
Affiliation  

A highly efficient synthesis of new chiral bisphosphanes derived from the renowned NORPHOS ligand is presented. The synthesis involves ring-opening metathesis of NORPHOS dioxide with an external olefin, followed by saturation of the new double bonds and adjustment of the oxidation level of phosphorus centers oxidation level. The synthesized bisphosphanes retain the configuration and enantiomeric purity of the starting NORPHOS. Their utility as ligands in asymmetric catalysis is exemplified using an open -NORPHOS ligand in some benchmark Rh-catalyzed hydrogenations of enamides where excellent chemical yields and enantiomeric purities of the products have been secured. The proposed protocol demonstrated the possibility of a straightforward synthesis of new chiral catalysts to be utilized in the asymmetric synthesis of pharmaceutically important compounds, such as amino acid derivatives.

中文翻译:

新型与NORPHOS相关的双膦的复分解方法:简便的合成及其在不对称氢化中的应用

提出了由著名的NORPHOS配体衍生的新型手性双膦的高效合成方法。合成过程包括使用外部烯烃使NORPHOS二氧化物开环易位,然后使新的双键饱和并调节磷中心的氧化水平。合成的双膦保持起始NORPHOS的构型和对映体纯度。在某些基准Rh催化的酰胺氢化反应中,使用开放的-NORPHOS配位体举例说明了它们在不对称催化中作为配体的效用,其中已确保了优异的化学收率和产物的对映体纯度。
更新日期:2021-04-29
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