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使用含亚砜的极化转移催化剂实现α-酮异己酸的可逆超极化

Reversible Hyperpolarization of Ketoisocaproate Using Sulfoxide-containing Polarization Transfer Catalysts.

作者信息

Tickner Ben J, Ahwal Fadi, Whitwood Adrian C, Duckett Simon B

机构信息

Centre for Hyperpolarisation in Magnetic Resonance, University of York, Heslington, York, U.K., YO10 5NY.

Department of Chemistry, University of York, Heslington, York, U.K., YO10 5DD.

出版信息

Chemphyschem. 2021 Jan 7;22(1):13-17. doi: 10.1002/cphc.202000825. Epub 2020 Nov 26.

DOI:10.1002/cphc.202000825
PMID:33196137
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7839500/
Abstract

The substrate scope of sulfoxide-containing magnetisation transfer catalysts is extended to hyperpolarize α-ketoisocaproate and α-ketoisocaproate-1-[ C]. This is achieved by forming [Ir(H) (κ -ketoisocaproate)(N-heterocyclic carbene)(sulfoxide)] which transfers latent magnetism from p-H via the signal amplification by reversible exchange (SABRE) process. The effect of polarization transfer field on the formation of enhanced C magnetization is evaluated. Consequently, performing SABRE in a 0.5 μT field enabled most efficient magnetisation transfer. C NMR signals for α-ketoisocaproate-1-[ C] in methanol-d are up to 985-fold more intense than their traditional Boltzmann derived signal intensity (0.8 % C polarisation). Single crystal X-ray diffraction reveals the formation of the novel catalyst decomposition products [Ir(μ-H)(H) (IMes)(SO(Ph)(Me) )] and [(Ir(H) (IMes)(SO(Me) )) (μ-S)] when the sulfoxides methylphenylsulfoxide and dimethylsulfoxide are used respectively.

摘要

含亚砜的磁化转移催化剂的底物范围扩展至使α-酮异己酸酯和α-酮异己酸酯-1-[¹³C]超极化。这是通过形成[Ir(H)(κ³-酮异己酸酯)(N-杂环卡宾)(亚砜)]来实现的，该化合物通过可逆交换信号放大(SABRE)过程从对映氢转移潜在磁性。评估了极化转移场对增强¹³C磁化形成的影响。因此，在0.5 μT场中进行SABRE可实现最有效的磁化转移。甲醇-d中α-酮异己酸酯-1-[¹³C]的¹³C NMR信号强度比其传统玻尔兹曼衍生信号强度高985倍(¹³C极化率为0.8%)。单晶X射线衍射表明，当分别使用亚砜甲基苯基亚砜和二甲基亚砜时，会形成新型催化剂分解产物[Ir(μ-H)(H)₂(IMes)(SO(Ph)(Me)₂)]和[(Ir(H)₂(IMes)(SO(Me)₂))₂(μ-S)]。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/9b9c80c60e1a/CPHC-22-13-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/78f2bb031636/CPHC-22-13-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/eb3f8195a02a/CPHC-22-13-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/6246b9e2d897/CPHC-22-13-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/140503f53cd5/CPHC-22-13-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/9b9c80c60e1a/CPHC-22-13-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/78f2bb031636/CPHC-22-13-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/eb3f8195a02a/CPHC-22-13-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/6246b9e2d897/CPHC-22-13-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/140503f53cd5/CPHC-22-13-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b21/7839500/9b9c80c60e1a/CPHC-22-13-g004.jpg

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