Effects of ligands on the migratory insertion of alkenes into rhodium–oxygen bonds

Richers, Casseday P.; Roediger, Sven; Laserna, Víctor; Hartwig, John F.

doi:10.1039/d0sc04402d

Cited by 9 publications

(8 citation statements)

References 59 publications

(67 reference statements)

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“…CO, alkene or alkyne) and an X-type ligand 2 (e.g. hydride, alkyl, aryl, alkenyl alkynyl, alkoxide [3][4][5] and amido 6 ). Specic examples include (1) the combination of carbonyl and hydrocarbyl ligands to give acyl groups, a vital step in the carbonylation of methanol to acetic acid 7 and the Pauson-Khand reaction [8][9][10] (2) reaction between a metal hydride and an alkene as part of a hydrogenation process 11 and (3) alkene insertion into a metal alkyl complex during polymerisation reactions.…”

Section: Introductionmentioning

confidence: 99%

A comprehensive understanding of carbon–carbon bond formation by alkyne migratory insertion into manganacycles

et al. 2022

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Section: Introductionmentioning

confidence: 99%

A comprehensive understanding of carbon–carbon bond formation by alkyne migratory insertion into manganacycles

et al. 2022

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“…39 Hartwig and coworkers have recently discussed the ligand effects on the migratory insertion step and demonstrated that the insertion step benefits from less electron-donating ligands. 40 On combining the data available, here we incorporated a relatively electron-poor diphenylphosphine ligand motif to mono-and bimetallic rhodium(I) complexes (Figure 1D). This yielded a set of active catalysts, which displayed significant bimetallic enhancement when used to facilitate an intermolecular hydrosilylation reaction.…”

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Bimetallic Rhodium Complexes: Precatalyst Activation-Triggered Bimetallic Enhancement for the Hydrosilylation Transformation

et al. 2023

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To explore how to access bimetallic catalysts that can outperform their monometallic analogues, a set of mono- and bimetallic NHC/phosphine (NHC = N-heterocyclic carbene)-ligated rhodium(I) complexes were designed, synthesized, and characterized. The complexes were used as catalysts for the intermolecular hydrosilylation of diphenylacetylene. All four catalysts displayed significantly faster catalytic rates than the related complexes reported previously containing NHC/pyrazolyl donor ligands. The bimetallic catalyst design led to enhanced catalytic activity over the monometallic analogue. The data revealed that the degree of bimetallic enhancement was highly dependent on the reaction conditions, coligands used, and the substrate addition order. The catalytic trends, in combination with mechanistic studies using individual substrates and density functional theory calculations, exposed that the bimetallic benefits were strongly linked to the catalyst activation procedure.

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“…Of particular note is the selection of the electron-deficient 1,2,3,4-tetramethyl-5-trifluoromethylcyclopenta-1,3-dienyl (Cp* CF3 ), which outperforms the prototypical pentamethylcyclopentadienyl (Cp*) ligand (Table , entry 2). Increased electron deficiency of the catalyst may aid migratory insertion into the alkene, resulting in higher reactivity. , Control reactions demonstrated that rhodium, i -PrOH, and K 2 CO 3 are all necessary components (Table , entries 4–6). We were pleased to observe that the hydroamidation product is still formed in synthetically useful yields when the equivalents of dioxazolone are reduced (2 equiv, 51%, Table , entry 7) and when the reaction is conducted without heating (55%, Table , entries 8).…”

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confidence: 99%

Rhodium(III)-Catalyzed Anti-Markovnikov Hydroamidation of Unactivated Alkenes Using Dioxazolones as Amidating Reagents

Wagner-Carlberg

Rovis

2022

J. Am. Chem. Soc.

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The amide is one of the most prevalent functional groups in all of pharmaceuticals, and for this reason, reactions that introduce the amide moiety are of particular value. Intermolecular hydroamidation of alkenes remains an underexplored method for the synthesis of amide-containing compounds. The majority of hydroamidation procedures exhibit Markovnikov regioselectivity, while current methods for anti-Markovnikov hydroamidation are somewhat limited to activated alkene substrates or radical processes. Herein, we report a general method for the intermolecular anti-Markovnikov hydroamidation of unactivated alkenes under mild conditions, utilizing Rh(III) catalysis in conjunction with dioxazolone amidating reagents and isopropanol as an environmentally friendly hydride source. The reaction tolerates a wide range of functional groups and efficiently converts electrondeficient alkenes, styrenes, and 1,1-disubstituted alkenes, in addition to unactivated alkenes, to their corresponding linear amides. Mechanistic studies reveal a reversible rhodium hydride migratory insertion step, leading to exquisite selectivity for the anti-Markovnikov product.

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Effects of ligands on the migratory insertion of alkenes into rhodium–oxygen bonds

Abstract: Insertions of olefins into metal-oxygen bonds are elementary steps of important catalytic processes, but well characterised complexes that undergo this reaction are rare, and little information on the effects of...

Cited by 9 publications

References 59 publications

A comprehensive understanding of carbon–carbon bond formation by alkyne migratory insertion into manganacycles

A comprehensive understanding of carbon–carbon bond formation by alkyne migratory insertion into manganacycles

Bimetallic Rhodium Complexes: Precatalyst Activation-Triggered Bimetallic Enhancement for the Hydrosilylation Transformation

Rhodium(III)-Catalyzed Anti-Markovnikov Hydroamidation of Unactivated Alkenes Using Dioxazolones as Amidating Reagents

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