Selective <i>cine</i> Substitution of 1‐Arylethenyl Acetates with Arylboron Reagents and a Diene/Rhodium Catalyst

Yu, Jung Yi; Shimizu, Ryosuke; Kuwano, Ryoichi

doi:10.1002/anie.201002745

Cited by 45 publications

(11 citation statements)

References 21 publications

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“…If 1,2-insertion occurs (pathway A), β-acetoxy elimination, followed by a Heck reaction type sequence, gives the alkenylation product. β-Acetoxy elimination has been proposed in many transition-metal-mediated processes . 2,1-Insertion of an alkenyl acetate to 36 (pathway B), followed by α-acetoxy elimination, may lead to the formation of a ruthenium carbene complex, in a way similar to a reaction reported by Caulton and co-workers, and this intermediate may also give the product by carbene C–H insertion and β-hydride elimination.…”

Section: Resultsmentioning

confidence: 79%

“…The stereochemical outcomes of these reactions cannot be explained simply by our proposed reaction mechanisms for the β-monosubstituted alkenyl acetates described in Figure , because alkenylation with ( Z )- 6h should give ( Z )- 7h , not ( E )- 7h . While β-hydride elimination is generally considered to proceed in a syn fashion, however, β-acetoxy elimination via both syn- and anti-periplanar transition states has been well documented in the literature . In particular, anti elimination may proceed selectively when ( E )-α,β-disubstituted olefins are obtained…”

Section: Resultsmentioning

confidence: 99%

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Ruthenium-Catalyzed Ortho-Selective C–H Alkenylation of Aromatic Compounds with Alkenyl Esters and Ethers

et al. 2013

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A direct, regioselective alkenylation of aromatic C–H bonds of aryl- and heteroarylpyridines and related compounds with alkenyl esters was developed using Ru(cod)(cot) as a catalyst. Aromatic compounds bearing electronically diverse substituents and various heterocyclic directing groups are reacted with alkenyl acetates bearing mono- and disubstituted alkenyl groups with aliphatic and aromatic substituents to give ortho-alkenylation products in high yields. The results of deuterium-labeling experiments and competition reactions using different ratios of the E and Z isomers of β-styryl acetate suggested that the C–H alkenylation proceeded via a ruthenium–alkene intermediate and the C–O bond of the alkenyl acetate was cleaved by β-acetoxy elimination. Two types of catalytically relevant species were identified, and the reactivities of these species, combined with the results of the kinetic studies, suggest that the rate-limiting step is the exchange of the COD ligand with the alkenyl ester. On the basis of the elucidated mechanism, the first catalytic coupling reaction using aromatic C–H bonds with C–O bonds of ethers was also developed.

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Section: Resultsmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Ruthenium-Catalyzed Ortho-Selective C–H Alkenylation of Aromatic Compounds with Alkenyl Esters and Ethers

et al. 2013

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“…Arylboronic esters 3a , 4a , 5a , 6a , and 3b – 3g were prepared according to the reference procedure.…”

Section: Methodsmentioning

confidence: 99%

Ru-Catalyzed Deoxygenative Regioselective C8–H Arylation of Quinoline N-Oxides

Kim

et al. 2019

J. Org. Chem.

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Regioselective C–H functionalization on quinolines is of high interest to lead to value-added products. Herein, we describe the development of Ru-catalyzed deoxygenative regioselective C8 arylation of quinoline N-oxides with arylboronic esters. Mechanistic studies revealed that it proceeds in a tandem process of arylation and then deoxygenation, wherein both steps were found to be catalytic with the ruthenium species.

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“…Following the general procedure D , compound 3f was obtained from 1-(3-methoxyphenyl)vinyl acetate (0.25 mmol, prepared according to literature procedure) and N -aminopyridinium salt 1b (0.3 mmol). The crude product was purified by column chromatography to afford 56 mg of compound 3f as a white solid (yield = 67%, 16 h).…”

Section: Methodsmentioning

confidence: 99%

Visible-Light-Mediated Amination of π-Nucleophiles with N-Aminopyridinium Salts

et al. 2019

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N-Aminopyridinium salts generate nitrogen-centered radicals by means of photoredox catalysis. Herein, we report that they can be trapped by enol equivalents to give α-amino carbonyl compounds in excellent yields. The broad synthetic utility of this method is demonstrated by functionalization of ketones, aldehydes, esters enol equivalents, vinyl ethers, and 1,3-diketones without the need for prior conversion to enol derivatives. The developed method is easily scalable, offers broad substrate scope, high chemoselectivity.

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Selective cine Substitution of 1‐Arylethenyl Acetates with Arylboron Reagents and a Diene/Rhodium Catalyst

Cited by 45 publications

References 21 publications

Ruthenium-Catalyzed Ortho-Selective C–H Alkenylation of Aromatic Compounds with Alkenyl Esters and Ethers

Ruthenium-Catalyzed Ortho-Selective C–H Alkenylation of Aromatic Compounds with Alkenyl Esters and Ethers

Ru-Catalyzed Deoxygenative Regioselective C8–H Arylation of Quinoline N-Oxides

Visible-Light-Mediated Amination of π-Nucleophiles with N-Aminopyridinium Salts

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