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微波辅助铑基多相催化剂还原醛酮的胺化反应。

Microwave-Assisted Reductive Amination of Aldehydes and Ketones Over Rhodium-Based Heterogeneous Catalysts.

机构信息

Department of Drug Science and Technology and NIS Interdepartmental Centre, University of Turin, Via Pietro Giuria 9, 10125, Turin, Italy.

Department of Chemistry, University of Milan, Via Golgi 19 - Corpo, A, 20133, Milan, Italy.

出版信息

Chempluschem. 2023 Mar;88(3):e202300017. doi: 10.1002/cplu.202300017.

DOI:10.1002/cplu.202300017
PMID:36971074
Abstract

Microwave (MW)-assisted reductive aminations of aldehydes and ketones were carried out in the presence of commercial and homemade heterogeneous Rh-based catalysts. Ultrasound (US) was used to improve dispersion and stability of metal nanoparticles, while commercial activated carbon and carbon nanofibers were used as supports. Moreover, various bio-derived molecules were selected as substrates, and aqueous ammonia was used as a cheap and non-toxic reagent. MW combined with heterogeneous Rh catalysts gave a 98.2 % yield in benzylamine at 80 °C with 10 bar H for 1 h; and a 43.3 % yield in phenylethylamine at 80 °C and 5 bar H for 2 h. Carbon nanofibers proved to be a better support for the metal active phase than simple activated carbon, since a limited yield in benzylamine (10.6 %) but a high selectivity for the reductive amination of ketones was obtained. Thus, raspberry ketone was converted to raspberry amine in a 63.0 % yield.

摘要

在商业和自制的均相 Rh 基催化剂存在下,进行了微波(MW)辅助的醛和酮的还原胺化反应。超声(US)用于改善金属纳米粒子的分散性和稳定性,而商业活性炭和碳纳米纤维则用作载体。此外,选择了各种生物衍生的分子作为底物,并用廉价且无毒的氨水溶液作为试剂。MW 与均相 Rh 催化剂结合,在 80°C、10 bar H 下反应 1 小时,可得到 98.2%的苄胺产率;在 80°C、5 bar H 下反应 2 小时,可得到 43.3%的苯乙胺产率。碳纳米纤维被证明是金属活性相的更好载体,因为得到的苄胺产率有限(10.6%),但酮的还原胺化具有很高的选择性。因此,覆盆子酮转化为覆盆子胺的产率为 63.0%。

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