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动力学分析揭示了在分子间催化不对称烯丙基溴酯化反应中克服副产物抑制作用。

Surmounting Byproduct Inhibition in an Intermolecular Catalytic Asymmetric Alkene Bromoesterification Reaction as Revealed by Kinetic Profiling.

机构信息

Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus, 82 Wood Lane, London W12 0BZ, U.K.

Department of Chemical Engineering, Imperial College London, South Kensington Campus, Imperial College Road, London SW7 2AZ, U.K.

出版信息

J Org Chem. 2023 Jul 7;88(13):8904-8914. doi: 10.1021/acs.joc.3c00672. Epub 2023 Jun 16.

DOI:10.1021/acs.joc.3c00672
PMID:37327488
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10337038/
Abstract

Kinetic profiling has shown that a (DHQD)PHAL-catalyzed intermolecular asymmetric alkene bromoesterification reaction is inhibited by primary amides, imides, hydantoins, and secondary cyclic amides, which are byproducts of common stoichiometric bromenium ion sources. Two approaches to resolving the inhibition are presented, enabling the (DHQD)PHAL loading to be dropped from 10 to 1 mol % while maintaining high bromoester conversions in 8 h or less. Iterative post-reaction recrystallizations enabled a homochiral bromonaphthoate ester to be synthesized using only 1 mol % (DHQD)PHAL.

摘要

动力学分析表明，（DHQD）PHAL 催化的烯基溴代酯的不对称分子间反应受到伯酰胺、酰亚胺、海因和仲环酰胺的抑制，这些物质是常见的定量溴鎓离子源的副产物。本文提出了两种解决抑制问题的方法，在 8 小时内保持高溴代酯转化率的情况下，（DHQD）PHAL 的负载量从 10 mol%降低到 1 mol%。通过反应后反复重结晶，仅使用 1 mol%（DHQD）PHAL 就可以合成手性溴萘酸酯。

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