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双铜和醛催化的苄胺的瞬态C-H磺酰化反应

Dual Copper- and Aldehyde-Catalyzed Transient C-H Sulfonylation of Benzylamines.

作者信息

Higham Joe I, Ma Tsz-Kan, Bull James A

机构信息

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

出版信息

Org Lett. 2023 Jul 21;25(28):5285-5290. doi: 10.1021/acs.orglett.3c01783. Epub 2023 Jul 13.

DOI:10.1021/acs.orglett.3c01783
PMID:37439636
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10367073/
Abstract

This study reports the first example of using a dual catalytic system with copper(II) acetate and 2-hydroxynicotinaldehyde to achieve transient C(sp)-H sulfonylation of benzylamines with sulfinate salts via a dynamically formed imine directing group. Manganese(IV) oxide was identified as an effective oxidant and base. Computational density functional theory investigations suggest that the transient directing group lowers the energy barrier for an acetate-mediated, turnover-limiting C-H activation step and subsequent combination of the cupracycle with a RSO radical.

摘要

本研究报道了首例使用醋酸铜（II）和2-羟基烟醛的双催化体系，通过动态形成的亚胺导向基团实现苄胺与亚磺酸盐的瞬态C(sp)-H磺酰化反应。二氧化锰（IV）被确定为有效的氧化剂和碱。密度泛函理论计算研究表明，瞬态导向基团降低了醋酸盐介导的、限制反应速率的C-H活化步骤以及随后的铜环与RSO自由基结合的能垒。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/8eef64dd4209/ol3c01783_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/685fc2552669/ol3c01783_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/a48ce51dd08f/ol3c01783_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/c273dc37af35/ol3c01783_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/ceb46afca51a/ol3c01783_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/8eef64dd4209/ol3c01783_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/685fc2552669/ol3c01783_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/a48ce51dd08f/ol3c01783_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/c273dc37af35/ol3c01783_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/ceb46afca51a/ol3c01783_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a425/10367073/8eef64dd4209/ol3c01783_0005.jpg

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本文引用的文献

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Transient directing ligands for selective metal-catalysed C-H activation.用于选择性金属催化C-H活化的瞬态导向配体
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Copper-Catalyzed Synthesis of Functionalized Aryl Sulfonamides from Sodium Sulfinates in Green Solvents.铜催化的绿色溶剂中由亚硫酸钠合成功能化芳基磺酰胺
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Amine-Catalyzed Copper-Mediated C-H Sulfonylation of Benzaldehydes via a Transient Imine Directing Group.
胺催化铜介导的通过瞬态亚胺导向基团的苯甲醛 C-H 磺酰化反应。
Angew Chem Int Ed Engl. 2022 Jul 4;61(27):e202202933. doi: 10.1002/anie.202202933. Epub 2022 May 5.
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Amino-oxetanes as amide isosteres by an alternative defluorosulfonylative coupling of sulfonyl fluorides.通过对磺酰氟的另一种脱氟磺酰化偶联反应，将氨基噁唑烷用作酰胺等排物。
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Advancing the Logic of Chemical Synthesis: C-H Activation as Strategic and Tactical Disconnections for C-C Bond Construction.推进化学合成的逻辑：C-H 活化作为 C-C 键构建的战略和策略性断键。
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