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使用甲基格氏试剂的烷基醇卤化反应。

Halogenation Reactions of Alkyl Alcohols Employing Methyl Grignard Reagents.

作者信息

Hirbawi Nadia, Lin Patricia C, Jarvo Elizabeth R

机构信息

Department of Chemistry, University of California, Irvine, California 92697-2025, United States.

出版信息

J Org Chem. 2022 Sep 16;87(18):12352-12369. doi: 10.1021/acs.joc.2c01590. Epub 2022 Sep 1.

DOI:10.1021/acs.joc.2c01590
PMID:36049783
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9486953/
Abstract

Grignard reagents are commonly used as carbanion equivalents. Herein, we report an example of Grignard reagents acting as halide nucleophiles to form alkyl iodides and bromides. We establish that Grignard reagents can convert alkyl mesylates into alkyl halides, as well as be employed in a one-pot halogenation reaction starting from alcohols, which proceed through mesylate intermediates. The halogenation reaction is confirmed to occur by an S2 pathway with inversion of configuration and is demonstrated to be efficient on multi-gram scale.

摘要

格氏试剂通常用作碳负离子等价物。在此，我们报道了格氏试剂作为卤化物亲核试剂形成烷基碘化物和溴化物的一个例子。我们证实格氏试剂可以将甲磺酸烷基酯转化为烷基卤化物，并且可用于从醇开始的一锅法卤化反应，该反应通过甲磺酸酯中间体进行。卤化反应被证实是通过构型翻转的S2途径发生的，并且在多克规模上被证明是有效的。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/480238aa192f/jo2c01590_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/4d38a38e1f8f/jo2c01590_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/eb0048967459/jo2c01590_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/81327cef4402/jo2c01590_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/480238aa192f/jo2c01590_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/4d38a38e1f8f/jo2c01590_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/eb0048967459/jo2c01590_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/81327cef4402/jo2c01590_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be91/9486953/480238aa192f/jo2c01590_0005.jpg

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