IRMOF-74(<i>n</i>)–Mg: a novel catalyst series for hydrogen activation and hydrogenolysis of C–O bonds

Stavila, Vitalie; Foster, Michael E.; Brown, Jonathan W.; Davis, Ryan W.; Benin, Annabelle I.; Zarkesh, Ryan A.; Parthasarathi, Ramakrishnan; Hoyt, David; Walter, Éric; Andersen, Amity; Washton, Nancy M.; Lipton, Andrew S.; Allendorf, Mark D.

doi:10.1039/c9sc01018a

Cited by 27 publications

(29 citation statements)

References 77 publications

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“…More importantly, by MOF or Pd/C as catalyst without a base, the selective hydrogenolysis with H 2 (10-30 bar) at 120-200°C resulted in no more than 55% yields (Fig. 1a, conditions C) [39][40][41] . In these studies, a large amount of reductant, strong base, and/or the low yield are/is still the limiting factor(s) for the applications.…”

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confidence: 99%

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Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature

Tan

Tian

et al. 2020

Nat Commun

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Cleavage of C–O bonds in lignin can afford the renewable aryl sources for fine chemicals. However, the high bond energies of these C–O bonds, especially the 4-O-5-type diaryl ether C–O bonds (~314 kJ/mol) make the cleavage very challenging. Here, we report visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by an acidolysis with an aryl carboxylic acid and a following one-pot hydrolysis. Two molecules of phenols are obtained from one molecule of diaryl ether at room temperature. The aryl carboxylic acid used for the acidolysis can be recovered. The key to success of the acidolysis is merging visible-light photoredox catalysis using an acridinium photocatalyst and Lewis acid catalysis using Cu(TMHD)2. Preliminary mechanistic studies indicate that the catalytic cycle occurs via a rare selective electrophilic attack of the generated aryl carboxylic radical on the electron-rich aryl ring of the diphenyl ether. This transformation is applied to a gram-scale reaction and the model of 4-O-5 lignin linkages.

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confidence: 99%

“…In recent years, selective hydrogenolysis under comparatively milder conditions was developed by Hartwig, Grubbs, Wang et al (Fig. 1a) [30][31][32][33][34][35][36][37][38][39][40][41] . The hydrogenolysis was accomplished by using [Ni], [Fe], or [Co] as catalyst, with H 2 (1-6 bar) or LiAlH 4 (2.5 equiv.)…”

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confidence: 99%

Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature

Tan

Tian

et al. 2020

Nat Commun

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“…27 Various commonly used metal ions in MOFs exhibit NMR-active isotopes with low natural abundance and small magnetic moments, for example 25 Mg and 67 Zn. [28][29][30] Special pulse sequences like CPMG (Carr-Purcell-Meiboom-Gill) can enhance the NMR signal thus enabling detection of such spectra. In addition, quadrupolar nuclei oen exhibit very broad lines.…”

Section: Solid-state Nmr Spectroscopy Of Mofsmentioning

confidence: 99%

Solid-state NMR spectroscopy: an advancing tool to analyse the structure and properties of metal–organic frameworks

Brunner

Rauche

2020

Chem. Sci.

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“…1A). [30][31][32][33][34][35][36][37][38][39][40][41] The hydrogenolysis was accomplished by using [Ni], [Fe], or…”

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confidence: 99%

“…1A, conditions c). [39][40][41] In these studies, a large amount of reductant, strong base, and/or the low yield are/is still the limited factor(s) for the applications.…”

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confidence: 99%

Visible-Light Photoredox-Catalyzed C–O Bond Cleavage of Diaryl Ethers by Acridinium Photocatalysts at Room Temperature

Tan

Tian

et al. 2020

Preprint

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We have developed visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by an acidolysis with an aryl car-boxylic acid and a following one-pot hydrolysis. Two phenols are obtained from a diaryl ether at room temperature. The aryl carboxylic acid used for the acidolysis can be recovered. The key to success of the acidolysis is merging visible-light photore-dox catalysis with a new acridinium photocatalyst and Lewic acid catalysis with Cu(TMHD)2. Preliminary mechanistic studies indicate that the catalytic cycle occurs via a rare selective electrophilic attack of the generated aryl carboxylic radical on the electron-rich aryl ring of diphenyl ether. This transformation is applied to a gram-scale reaction and the model of 4-O-5 lignin linkages.

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IRMOF-74(n)–Mg: a novel catalyst series for hydrogen activation and hydrogenolysis of C–O bonds

Abstract: Non-monotonic catalytic behavior in an isoreticular MOF series results from subtle structural differences that alter the substrate binding energy.

Cited by 27 publications

References 77 publications

Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature

Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature

Solid-state NMR spectroscopy: an advancing tool to analyse the structure and properties of metal–organic frameworks

Visible-Light Photoredox-Catalyzed C–O Bond Cleavage of Diaryl Ethers by Acridinium Photocatalysts at Room Temperature

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