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通过形成镁中间体,在含酸性质子的取代基溴杂环上进行卤-金属交换。

Halogen-Metal Exchange on Bromoheterocyclics with Substituents Containing an Acidic Proton via Formation of a Magnesium Intermediate.

机构信息

Pharmacy College, Chongqing Medical University, Chongqing 400016, China.

出版信息

Molecules. 2017 Nov 11;22(11):1952. doi: 10.3390/molecules22111952.

DOI:10.3390/molecules22111952
PMID:29137130
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6150384/
Abstract

A selective and practical bromine-metal exchange on bromoheterocyclics bearing substituents with an acidic proton under non-cryogenic conditions was developed by a simple modification of an existing protocol. Our protocol of using a combination of i-PrMgCl and n-BuLi has not only solved the problem of intermolecular quenching that often occurred when using alkyl lithium alone as the reagent for halogen-lithium exchange, but also offered a highly selective method for performing bromo-metal exchange on dibrominated arene compounds through chelation effect.

摘要

在非低温条件下,通过对带有酸性质子取代基的溴杂环进行选择性和实用的溴-金属交换反应,对现有方案进行了简单的改进。我们使用 i-PrMgCl 和 n-BuLi 的组合的方案不仅解决了单独使用烷基锂作为卤-锂交换试剂时经常发生的分子间猝灭问题,而且还通过螯合效应提供了一种在二溴芳烃化合物上进行溴-金属交换的高度选择性方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/d5c95352020f/molecules-22-01952-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/c9c56fb4b2b7/molecules-22-01952-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/3d187148ce69/molecules-22-01952-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/d5c95352020f/molecules-22-01952-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/c9c56fb4b2b7/molecules-22-01952-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/3d187148ce69/molecules-22-01952-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb36/6150384/d5c95352020f/molecules-22-01952-sch003.jpg

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本文引用的文献

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An efficient Au-catalyzed synthesis of isomukonidine, clausine L, mukonidine, glycosinine, mukonal, and clausine V from propadienyl methyl ether.一种从丙二烯基甲基醚高效合成异木香碱、克劳辛 L、木香碱、糖核酸、木香烷和克劳辛 V 的金催化方法。
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Total synthesis of (+)-phorboxazole A exploiting the Petasis-Ferrier rearrangement.利用佩塔西斯-费里尔重排反应全合成(+)-佛波醇酯A
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Selective halogen-magnesium exchange reaction via organomagnesium ate complex.通过有机镁酸根络合物进行的选择性卤素-镁交换反应。
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Halogen-Magnesium Exchange via Trialkylmagnesates for the Preparation of Aryl- and Alkenylmagnesium Reagents This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports, and Culture, Japan.通过三烷基镁酸盐进行卤素-镁交换制备芳基和烯基镁试剂 本研究得到了日本文部科学省科学研究资助金的支持。
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