Mora Vargas Jorge Andrés, Burtoloso Antonio C B
Institute of Chemistry of São Carlos, University of São Paulo, São Carlos, São Paulo, CEP, 13560-970, Brazil.
ChemSusChem. 2023 Dec 7;16(23):e202300936. doi: 10.1002/cssc.202300936. Epub 2023 Sep 27.
The present study highlights a novel and advantageous protocol for accessing carbamates through the well-established three-component coupling reaction involving CO , amines, and alkyl halides. By employing an immobilized organic base, operating under mild reaction conditions, an array of alkyl carbamates in yields of up to 95 % could be isolated. This approach offers a broad and versatile product scope, allowing for the facile modification of both the amine and alkyl halide reactants. Notably, the pioneering use of an immobilized organic base, specifically the polymer-supported 1,8-diazabicyclo[5.4.0]undec-7-ene (PS-DBU), in this three-component reaction eliminates the need for classical purification steps, streamlining the process. To ensure practicality and sustainability, extensive studies were conducted to verify the recovery and reusability of the polymer-supported DBU catalyst, which consistently maintained the high chemical yield of the carbamates across multiple cycles. Overall, this innovative protocol represents a significant advancement in carbamate synthesis, combining efficiency, generality, and the potential for DBU recycling.
本研究突出了一种新颖且有利的方案，可通过涉及一氧化碳、胺和卤代烃的成熟三组分偶联反应来制备氨基甲酸酯。通过使用固定化有机碱，在温和的反应条件下操作，可以分离出一系列产率高达95%的烷基氨基甲酸酯。这种方法提供了广泛且通用的产物范围，使得胺和卤代烃反应物都能轻松改性。值得注意的是，在这种三组分反应中首次使用固定化有机碱，特别是聚合物负载的1,8-二氮杂双环[5.4.0]十一碳-7-烯（PS-DBU），无需传统的纯化步骤，简化了工艺。为确保实用性和可持续性，进行了广泛研究以验证聚合物负载的DBU催化剂的回收和可重复使用性，该催化剂在多个循环中始终保持氨基甲酸酯的高化学产率。总体而言，这种创新方案代表了氨基甲酸酯合成的重大进展，兼具效率、通用性以及DBU回收的潜力。
