Liu Yongzhuang, Afanasenko Anastasiia, Elangovan Saravanakumar, Sun Zhuohua, Barta Katalin
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Key Laboratory of Bio-Based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, People's Republic of China.
ACS Sustain Chem Eng. 2019 Jul 1;7(13):11267-11274. doi: 10.1021/acssuschemeng.9b00619. Epub 2019 May 31.
Primary benzylamines are highly important building blocks in the pharmaceutical and polymer industry. An attractive catalytic approach to access these compounds is the direct coupling of benzyl alcohols with ammonia via the borrowing hydrogen methodology. However, this approach is usually hampered by a series of side-reactions, one of the most prominent being the overalkylation of the formed primary amine. Herein, we describe a robust catalytic methodology, which utilizes commercially available heterogeneous Ni catalysts and easy-to-handle ammonia sources, such as aqueous ammonia or ammonium salts, for the formation of primary benzylamines with good selectivity and scope. Notably, our method enables the conversion of potentially lignin-derived vanillyl alcohol to vanillylamine, which can be used to produce emerging biobased polymers or as pharma building blocks. Important sugar derived platform alcohols as well as long chain aliphatic primary alcohols can be successfully aminated. Moreover, we provide an alternative, sustainable route to -xylylenediamine and -xylylenediamine, important components of heat resistant polyamides such as Kevlar.
伯苄胺是制药和聚合物工业中非常重要的结构单元。一种制备这些化合物的有吸引力的催化方法是通过借氢法将苄醇与氨直接偶联。然而，这种方法通常受到一系列副反应的阻碍，其中最突出的一个是所形成的伯胺的过度烷基化。在此，我们描述了一种稳健的催化方法，该方法利用市售的多相镍催化剂和易于处理的氨源，如水氨或铵盐，以良好的选择性和适用范围制备伯苄胺。值得注意的是,我们的方法能够将潜在的木质素衍生香草醇转化为香草胺，其可用于生产新兴的生物基聚合物或作为药物结构单元。重要的糖衍生平台醇以及长链脂肪族伯醇都可以成功地进行胺化。此外，我们提供了一条制备对苯二甲撑二胺和间苯二甲撑二胺的可持续替代路线，它们是诸如凯夫拉尔等耐热聚酰胺的重要成分。
