Palladium(<scp>ii</scp>)-catalyzed γ-selective hydroarylation of alkenyl carbonyl compounds with arylboronic acids

Matsuura, Rei; Jankins, Tanner C.; Hill, David E.; Yang, Kin S.; Gallego, Gary M.; Yang, Shouliang; He, Minqiang; Wang, Fen; Marsters, Rohan P.; McAlpine, Indrawan; Engle, Keary M.

doi:10.1039/c8sc03081b

Cited by 72 publications

(24 citation statements)

References 46 publications

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“…Transmetalation of aryl metal reagents with a palladium( ii ) catalyst to generate the Ar–PdX intermediate has been well documented 7. In recent years, several groups have developed an array of methods for alkene functionalization triggered by Pd II -catalyzed transmetalation of arylboronic acids such as the oxidative boron Heck reaction 8,9. We thus questioned whether three-component heterodiarylation of olefins with aryl halides and arylboronic acids could also be initiated by a transmetalation step (Scheme 1c, lower panel).…”

Section: Introductionmentioning

confidence: 99%

Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids

2019

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Section: Introductionmentioning

confidence: 99%

Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids

2019

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“…It should be mentioned that a small amount of C2‐deuterated products were detected when using D 2 O or PhB(OD) 2 as the source of deuterons in control experiments, [8] indicating that both H 2 O and BF(OH) 2 could be a competent proton donor in addition to acetic acid. However, the located transition state of the protodepalladation step with either H 2 O or BF(OH) 2 as proton donor is quite high‐lying in terms of free‐energy barriers (see Figure S1 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…Addition across the double bond of α,β‐enones has been easily realized, [5] while the hydroarylation of the less active β,γ‐vinylketones has been achieved using the AQ directing strategy [8] . Can the AQ directing strategy be expanded to the hydroarylation of α,β‐ and γ,δ‐vinyl carbonyls?…”

Section: Resultsmentioning

confidence: 99%

DFT Mechanistic Study on Palladium‐Catalyzed Redox‐Neutral Hydroarylation of Unactivated Alkenes with Arylboronic Acids

Zhou

et al. 2021

Asian J Org Chem

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Density functional calculations were carried out on the mechanism of a palladium‐catalyzed hydroarylation reaction of β,γ‐unsaturated carbonyl compounds with arylboronic acids reported by Engle's group. The proposed reaction pathway consists of several key mechanistic steps, including the chelation of substrate 1 a, transmetalation of organoboron 2 a, migratory insertion, protodepalladation, and dechelation of product 3 a, among which the transmetalation step is rate‐determining with a free‐energy barrier of 27.0 kcal/mol. Experimental researchers proposed that the chelation of Daugulis's 8‐aminoquinoline (AQ) directing group facilitated the desired hydroarylation in a γ‐selective manner. However, the present study revealed that the chelation of AQ indeed retarded the delivery of the aryl group to the double bond and the regioselectivity was not necessarily the result of this group. Indeed, it could effectively prevent the homocoupling of 2 a, because the homocoupling was predicted to be easier than the desired hydroarylation in the absence of AQ. Additionally, some reductive coupling pathways between 1 a and 2 a were designed, and the competition of them was discussed in great detail. Lastly, the extension of this synthetic strategy to other types of alkenes was predicted.

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“…The synthesis of nocardiolactone was also described in this paper. The palladium-catalyzed γ-selective hydroarylation of a β,γ-unsaturated secondary amide was reported by Engle (Table 11, entry 3) [192]. In his report, palladium acetate was used to catalyze a regioselective hydroarylation with arylboronic acids, although the substrate scope was limited to amides bearing the N -8-aminoquinoline (AQ) substituent.…”

Section: Chemical Transformations Of Indolylboronic Acid Derivativesmentioning

confidence: 99%

Indolylboronic Acids: Preparation and Applications

et al. 2019

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Indole derivatives are associated with a variety of both biological activities and applications in the field of material chemistry. A number of different strategies for synthesizing substituted indoles by means of the reactions of indolylboronic acids with electrophilic compounds are considered the methods of choice for modifying indoles because indolylboronic acids are easily available, stable, non-toxic and new reactions using indolylboronic acids have been described in the literature. Thus, the aim of this review is to summarize the methods available for the preparation of indolylboronic acids as well as their chemical transformations. The review covers the period 2010–2019.

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Palladium(ii)-catalyzed γ-selective hydroarylation of alkenyl carbonyl compounds with arylboronic acids

Abstract: A catalytic γ-selective syn-hydroarylation of alkenyl carbonyl compounds using arylboronic acids has been developed using a substrate directivity approach with a palladium(ii) catalyst.

Cited by 72 publications

References 46 publications

Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids

Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids

DFT Mechanistic Study on Palladium‐Catalyzed Redox‐Neutral Hydroarylation of Unactivated Alkenes with Arylboronic Acids

Indolylboronic Acids: Preparation and Applications

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