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在2-甲基四氢呋喃存在下烯烃的无催化剂氢磷化反应:一种绿色且简便地制备多种叔膦的方法。

Catalyst-free hydrophosphination of alkenes in presence of 2-methyltetrahydrofuran: a green and easy access to a wide range of tertiary phosphines.

作者信息

Bissessar Damien, Egly Julien, Achard Thierry, Steffanut Pascal, Bellemin-Laponnaz Stéphane

机构信息

Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg, CNRS UMR 7504 23 Rue du Loess, BP 43 F-67034 Strasbourg Cedex 2 France

CLARIANT Plastics and Coatings AG Rothausstrasse 61 4132 Muttenz Switzerland.

出版信息

RSC Adv. 2019 Aug 30;9(47):27250-27256. doi: 10.1039/c9ra04896k. eCollection 2019 Aug 29.

Abstract

A hydrophosphination reaction that is free of base, acid and catalyst, using only 2-methyltetrahydrofuran as additive has been performed. A new family of mono-, di-, tri- and tetra-phosphines compounds are obtained in good to excellent yields by adding diphenylphosphine to alkenes, mono- and polyfunctional acrylics (based on acrylate and methacrylate motifs) and acrylamide substrates. Addition of four equivalent of bio-mass derived 2-MeTHF into the reaction media improves both conversion and time of the reaction and reduces the sensitivity of the reactants over oxidation. This simple, straightforward and atom-economic method respects the principles of Green Chemistry. Furthermore, in each case this transformation shows an exclusive regioselectivity towards the anti-Markovnikov products.

摘要

已经进行了一种无碱、无酸且无催化剂的氢膦化反应,仅使用2-甲基四氢呋喃作为添加剂。通过将二苯基膦添加到烯烃、单官能和多官能丙烯酸酯(基于丙烯酸酯和甲基丙烯酸酯基团)以及丙烯酰胺底物中,以良好至优异的产率获得了一个新的单膦、二膦、三膦和四膦化合物家族。向反应介质中添加四当量生物质衍生的2-MeTHF可提高反应的转化率和时间,并降低反应物对氧化的敏感性。这种简单、直接且原子经济的方法符合绿色化学原则。此外,在每种情况下,这种转化对反马氏产物都表现出独特的区域选择性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/323c/9070578/719d9dba4e28/c9ra04896k-s1.jpg

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