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铱催化的 C1 取代氧杂苯并降冰片二烯与水杨醛的氢酰化反应：一项实验与计算研究

Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study.

作者信息

Ho Angel, Pounder Austin, Valluru Krish, Chen Leanne D, Tam William

机构信息

Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada.

出版信息

Beilstein J Org Chem. 2022 Mar 2;18:251-261. doi: 10.3762/bjoc.18.30. eCollection 2022.

DOI:10.3762/bjoc.18.30
PMID:35330776
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8919423/
Abstract

An experimental and theoretical investigation on the iridium-catalyzed hydroacylation of C-substituted oxabenzonorbornadienes with salicylaldehyde is reported. Utilizing commercially available [Ir(COD)Cl] in the presence of 5 M KOH in dioxane at 65 °C, provided a variety of hydroacylated bicyclic adducts in up to a 95% yield with complete stereo- and regioselectivity. The mechanism and origins of selectivity in the iridium-catalyzed hydroacylation reaction has been examined at the M06/Def2TZVP level of theory. The catalytic cycle consists of three key steps including oxidative addition into the aldehyde C-H bond, insertion of the olefin into the iridium hydride, and C-C bond-forming reductive elimination. Computational results indicate the origin of regioselectivity is involved in the reductive elimination step.

摘要

报道了关于铱催化C-取代的氧杂苯并降冰片二烯与水杨醛进行氢酰化反应的实验和理论研究。在65℃下，于二氧六环中使用市售的[Ir(COD)Cl]并存在5 M KOH，可提供多种氢酰化双环加合物，产率高达95%，且具有完全的立体和区域选择性。在理论水平M06/Def2TZVP上研究了铱催化氢酰化反应中选择性的机理和起源。催化循环包括三个关键步骤，即氧化加成到醛的C-H键、烯烃插入到铱氢化物中以及形成C-C键的还原消除。计算结果表明区域选择性的起源与还原消除步骤有关。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/ceb24d63471b/Beilstein_J_Org_Chem-18-251-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/8690cab6a16c/Beilstein_J_Org_Chem-18-251-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/bc5362732ed5/Beilstein_J_Org_Chem-18-251-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/3fab8abae9b3/Beilstein_J_Org_Chem-18-251-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/6096364326f2/Beilstein_J_Org_Chem-18-251-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/4977cb441379/Beilstein_J_Org_Chem-18-251-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/a6820ad4c6e9/Beilstein_J_Org_Chem-18-251-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/ceb24d63471b/Beilstein_J_Org_Chem-18-251-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/8690cab6a16c/Beilstein_J_Org_Chem-18-251-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/bc5362732ed5/Beilstein_J_Org_Chem-18-251-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/3fab8abae9b3/Beilstein_J_Org_Chem-18-251-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/6096364326f2/Beilstein_J_Org_Chem-18-251-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/4977cb441379/Beilstein_J_Org_Chem-18-251-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/a6820ad4c6e9/Beilstein_J_Org_Chem-18-251-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/85d7/8919423/ceb24d63471b/Beilstein_J_Org_Chem-18-251-g005.jpg

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