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为什么硫脲类和方酰胺会减缓爱尔兰-克莱森重排反应？

Why do thioureas and squaramides slow down the Ireland-Claisen rearrangement?

作者信息

Krištofíková Dominika, Filo Juraj, Mečiarová Mária, Šebesta Radovan

机构信息

Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Mlynská dolina, Ilkovičova 6, 84215 Bratislava, Slovakia.

Institute of Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Mlynská dolina, Ilkovičova 6, 84215 Bratislava, Slovakia.

出版信息

Beilstein J Org Chem. 2019 Dec 10;15:2948-2957. doi: 10.3762/bjoc.15.290. eCollection 2019.

DOI:10.3762/bjoc.15.290
PMID:31921366
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6941421/
Abstract

A range of chiral hydrogen-bond-donating organocatalysts was tested in the Ireland-Claisen rearrangement of silyl ketene acetals. None of these organocatalysts was able to impart any enantioselectivity on the rearrangements. Furthermore, these organocatalysts slowed down the Ireland-Claisen rearrangement in comparison to an uncatalyzed reaction. The catalyst-free reaction proceeded well in green solvents or without any solvent. DFT calculations showed that the activation barriers are higher for reactions involving hydrogen-donating organocatalysts and kinetic experiments suggest that the catalysts bind stronger to the starting silyl ketene acetals than to transition structures thus leading to inefficient rearrangement reactions.

摘要

一系列手性氢键供体有机催化剂在硅基烯酮缩醛的爱尔兰-克莱森重排反应中进行了测试。这些有机催化剂均无法使重排反应产生任何对映选择性。此外，与未催化的反应相比，这些有机催化剂减缓了爱尔兰-克莱森重排反应的速度。无催化剂的反应在绿色溶剂中或无任何溶剂的情况下进行良好。密度泛函理论计算表明，涉及氢键供体有机催化剂的反应的活化能垒更高，动力学实验表明，催化剂与起始硅基烯酮缩醛的结合强于与过渡结构的结合，从而导致重排反应效率低下。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/cef2cfc8d2b4/Beilstein_J_Org_Chem-15-2948-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/ac4631967967/Beilstein_J_Org_Chem-15-2948-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/577f77c2bf0d/Beilstein_J_Org_Chem-15-2948-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/9eb726993dad/Beilstein_J_Org_Chem-15-2948-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/1a4c065f5e40/Beilstein_J_Org_Chem-15-2948-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/449cd9064911/Beilstein_J_Org_Chem-15-2948-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/08b473685bb4/Beilstein_J_Org_Chem-15-2948-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/8a13cad5898f/Beilstein_J_Org_Chem-15-2948-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/cef2cfc8d2b4/Beilstein_J_Org_Chem-15-2948-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/ac4631967967/Beilstein_J_Org_Chem-15-2948-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/577f77c2bf0d/Beilstein_J_Org_Chem-15-2948-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/9eb726993dad/Beilstein_J_Org_Chem-15-2948-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/1a4c065f5e40/Beilstein_J_Org_Chem-15-2948-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/449cd9064911/Beilstein_J_Org_Chem-15-2948-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/08b473685bb4/Beilstein_J_Org_Chem-15-2948-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/8a13cad5898f/Beilstein_J_Org_Chem-15-2948-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fca0/6941421/cef2cfc8d2b4/Beilstein_J_Org_Chem-15-2948-g006.jpg

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Speeding Up Sigmatropic Shifts-To Halve or to Hold.促进 σ 迁移反应——减半还是维持。
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