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用于控制氢甲酰化催化活性和选择性的超分子方法。

Supramolecular Approaches To Control Activity and Selectivity in Hydroformylation Catalysis.

作者信息

Nurttila Sandra S, Linnebank Pim R, Krachko Tetiana, Reek Joost N H

机构信息

Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands.

出版信息

ACS Catal. 2018 Apr 6;8(4):3469-3488. doi: 10.1021/acscatal.8b00288. Epub 2018 Mar 9.

DOI:10.1021/acscatal.8b00288
PMID:29657887
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5894442/
Abstract

The hydroformylation reaction is one of the most intensively explored reactions in the field of homogeneous transition metal catalysis, and many industrial applications are known. However, this atom economical reaction has not been used to its full potential, as many selectivity issues have not been solved. Traditionally, the selectivity is controlled by the ligand that is coordinated to the active metal center. Recently, supramolecular strategies have been demonstrated to provide powerful complementary tools to control activity and selectivity in hydroformylation reactions. In this review, we will highlight these supramolecular strategies. We have organized this paper in sections in which we describe the use of supramolecular bidentate ligands, substrate preorganization by interactions between the substrate and functional groups of the ligands, and hydroformylation catalysis in molecular cages.

摘要

氢甲酰化反应是均相过渡金属催化领域中研究最为深入的反应之一,并且已知有许多工业应用。然而,由于许多选择性问题尚未解决,这种原子经济反应尚未得到充分利用。传统上,选择性由与活性金属中心配位的配体控制。最近,超分子策略已被证明是控制氢甲酰化反应活性和选择性的强大补充工具。在这篇综述中,我们将重点介绍这些超分子策略。我们将本文分为几个部分,在这些部分中,我们描述了超分子双齿配体的使用、底物与配体官能团之间的相互作用对底物的预组织作用以及分子笼中的氢甲酰化催化作用。

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Angew Chem Int Ed Engl. 2017 Aug 21;56(35):10564-10568. doi: 10.1002/anie.201705467. Epub 2017 Jul 24.
4
Tuning the Porphyrin Building Block in Self-Assembled Cages for Branched-Selective Hydroformylation of Propene.在自组装笼中调节卟啉结构单元用于丙烯的支链选择性氢甲酰化反应
Chemistry. 2017 Oct 20;23(59):14769-14777. doi: 10.1002/chem.201702113. Epub 2017 Aug 17.
5
Harnessing non-covalent interactions to exert control over regioselectivity and site-selectivity in catalytic reactions.利用非共价相互作用来控制催化反应中的区域选择性和位点选择性。
Chem Sci. 2017 Feb 1;8(2):864-877. doi: 10.1039/c6sc04157d. Epub 2016 Oct 5.
6
Unexpected CO Dependencies, Catalyst Speciation, and Single Turnover Hydrogenolysis Studies of Hydroformylation via High Pressure NMR Spectroscopy.通过高压 NMR 光谱研究高压下通过高压 NMR 光谱研究氢甲酰化反应中的意外 CO 依赖性、催化剂形态和单程氢解
J Am Chem Soc. 2017 Feb 22;139(7):2778-2785. doi: 10.1021/jacs.6b12533. Epub 2017 Feb 8.
7
Rhodium-Catalyzed Hydroformylation of 1,1-Disubstituted Allenes Employing the Self-Assembling 6-DPPon System.铑催化的 1,1-二取代烯丙基化合物的氢甲酰化反应采用自组装的 6-DPPon 体系。
Angew Chem Int Ed Engl. 2015 Jun 1;54(23):6913-7. doi: 10.1002/anie.201502086. Epub 2015 Apr 27.
8
Supramolecular catalysis in metal-ligand cluster hosts.金属-配体簇主体中的超分子催化作用。
Chem Rev. 2015 May 13;115(9):3012-35. doi: 10.1021/cr4001226. Epub 2015 Apr 21.
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Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage.超分子金属笼中铑催化剂的对映选择性氢甲酰化作用。
J Am Chem Soc. 2015 Feb 25;137(7):2680-7. doi: 10.1021/ja512637k. Epub 2015 Feb 11.
10
Transition metal catalysis in confined spaces.受限空间中的过渡金属催化作用。
Chem Soc Rev. 2015 Jan 21;44(2):433-48. doi: 10.1039/c4cs00192c.