127154-57-8

Upstream product

• 2553-04-0 ortho-methoxybenzophenone 
• 67-56-1 methanol 
• 16567-18-3 8-bromoquinoline 
• 615-36-1 2-bromoaniline 
• 1829-34-1 2-hydroxy-3-bromobenzaldehyde 
• 88275-87-0 3-bromo-2-methyloxybenzaldehyde 
• 20143-53-7 2-(2-iodophenoxy)-1-phenylethan-1-one 
• 70-11-1 α-bromoacetophenone 
• 533-58-4 2-Iodophenol 
• 42434-88-8 2-(2-bromophenoxy)-1-phenyl-1-ethanone 
• 1018669-08-3 tert-butyl(dimethyl)[2-(1-phenylvinyl)phenoxy]silane 
• 923594-99-4 2-(2-oxo-2-phenyl-ethoxy)-phenyl boronic acid 
• 923594-93-8 2-(2-iodo-phenoxy)-1-phenyl-ethanone ethylene acetal 

Relevant academic research and scientific papers

Nickel-Catalyzed Asymmetric Addition of Aromatic Halides to Ketones: Highly Enantioselective Synthesis of Chiral 2,3-Dihydrobenzofurans Containing a Tertiary Alcohol

A highly enantioselective and straightforward synthetic procedure to chiral 3-hydroxy-2,3-dihydrobenzofurans has been developed by nickel/bisoxazoline-catalyzed intramolecular asymmetric addition of aryl halides to unactivated ketones, giving 2,3-dihydrobenzofurans with a chiral tertiary alcohol at the C-3 position in good yields and excellent enantioselectivities (up to 92percent yield and 98percent ee). The gram-scale reaction also proceeded smoothly without a loss of yield and enantioselectivity.

Redox-Neutral Coupling between Two C(sp3)?H Bonds Enabled by 1,4-Palladium Shift for the Synthesis of Fused Heterocycles

The intramolecular coupling of two C(sp3)?H bonds to forge a C(sp3)?C(sp3) bond is enabled by 1,4-Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)?C(sp3) cross-dehydrogenative couplings, this reaction operates under redox-neutral conditions, with the C?Br bond acting as an internal oxidant. Furthermore, it allows the coupling between two moderately acidic primary or secondary C?H bonds, which are adjacent to an oxygen or nitrogen atom on one side, and benzylic or adjacent to a carbonyl group on the other side. A variety of valuable fused heterocycles were obtained from easily accessible ortho-bromophenol and aniline precursors. The second C?H bond cleavage was successfully replaced with carbonyl insertion to generate other types of C(sp3)-C(sp3) bonds.

Development and Mechanistic Study of Quinoline-Directed Acyl C-O Bond Activation and Alkene Oxyacylation Reactions

The intramolecular addition of both an alkoxy and acyl substituent across an alkene, oxyacylation of alkenes, using rhodium catalyzed C-O bond activation of an 8-quinolinyl ester is described. Our unsuccessful attempts at intramolecular carboacylation of ketones via C-C bond activation ultimately informed our choice to pursue and develop the intramolecular oxyacylation of alkenes via quinoline-directed C-O bond activation. We provide a full account of our catalyst discovery, substrate scope, and mechanistic experiments for quinoline-directed alkene oxyacylation.

Reductive cyclization of halo-ketones to form 3-hydroxy-2-oxindoles via palladium catalyzed hydrogenation: a hydrogen-mediated Grignard addition

Abstract The reductive cyclization of N-oxoacyl ortho-bromoanilides to form 3-hydroxy-2-oxindoles under the conditions of palladium catalyzed hydrogenation is described. This work may be viewed as a prelude to intermolecular hydrogen-mediated Grignard-typ

Benzofurans from benzophenones and dimethylacetamide: Copper-promoted cascade formation of furan O1-C2 and C2-C3 bonds under oxidative conditions

DMA donates: Copper(II) acetate and 8-hydroxyquinoline promote the formation of a benzofuran core through a cascade of copper-catalyzed processes wherein the key carbon atom comes from the dimethylacetamide (DMA) solvent. Strong evidence for the participation of a Wacker cyclization catalyzed solely by copper is provided, not only in the title reaction from benzophenones but also from 2-hydroxy-α-arylstyrene derivatives. Copyright

Palladium(II)-catalyzed intramolecular addition of arylboronic acids to ketones

A palladium(II)-catalyzed intramolecular addition of arylboronic acids to ketones was developed. Compared to Pd(OAc)2 catalysis system, cationic palladium complex with dppp as the ligand has higher catalytic activity and efficiency for wider sc

Cationic palladium complex catalyzed highly enantioselective intramolecular addition of arylboronic acids to ketones. A convenient synthesis of optically active cycloalkanols

An efficient and convenient synthesis of optically active cycloalkanols by utilizing the chiral cationic palladium complex as the catalyst was achieved in mild conditions with high yield and high enantioselectivity. Copyright

Photocyclization Reactions. Part 6 [1]. Solvent and Substituent Effects in the Synthesis of Dihydrobenzofuranols Using Photocyclization of 2-Alkoxybenzophenones and Ethyl 2-Benzoylphenoxyacetates

Photocyclization reactions were carried out on 2-alkoxybenzophenones 1a-h and ethyl 2-benzoylphenoxyacetates 5a-e in three solvents of different polarity (benzene, acetonitrile and methanol) to examine solvent and substituent effects on the cyclization of 1,5-biradical intermediates to dihydrobenzofuranols. Irradiation of 1a-f in benzene gave dihydrobenzofuranols 4a-f in 80-94% yields. The ratios of cis-and trans-isomers of 4b-f were 12:1 to 1:0, showing stereoselective formation of cis-isomers. On the other hand, irradiation of 1a-f in acetonitrile and methanol gave 4a-f in 68-81% and 7-75% yields, respectively. However, the ratios of cis- and trans-isomers of 4b-f were 3.5:1 to 1.3:1 in acetonitrile and 2.0:1 to 1:1.7 in methanol, showing decreased stereoselectivity. The decrease in stereoselectivity was attributed to intermolecular hydrogen bonding between the hydroxyl group of 1,5-biradicals and solvents (acetonitrile and methanol). Similarly, irradiation of 5a-e in benzene afforded cis-dihydrobenzofuranols cis-11a-e stereoselectively. In contrast, irradiation of 5a-e in acetonitrile and methanol gave a mixture of cis- and trans-isomers of 11a-e because of intermolecular hydrogen bonding between the hydroxyl group of 1,5-biradicals and solvents. The cis and Irons ratios of 11a-e varied from 1.5:1 to 17.8:1 in acetonitrile and from 2.6:1 to 1:4.5 in methanol. Solvent and substituent effects on the cyclization of 1,5-biradicals and reaction pathways are discussed.

Photocyclization Reactions. Part 5 [1]. Synthesis of Dihydrobenzofuranols Using Photocyclization of 2-Alkoxybenzophenones and Ethyl 2-Benzoylphenoxyacetates

Photocyclization reactions were carried out on 2-alkoxybenzophenones 1a-h and ethyl 2-benzoylphenoxyacetates 2a-e in acetonitrile. Irradiation of 1a-h gave dihydrobenzofuranols 4a-h in 68-84% yields. Similarly, irradiation of 2a-e afforded dihydrobenzofuranols 8a-e in 72-75% yields. Ethyl acrylates 9b-c were also produced in 6-8% yields from photoreactions of 2b-c. Substituent effects on cyclization of 1,5-biradical intermediates and reaction pathways are discussed. Benzophenones are useful compounds to prepare dihydrobenzofuranols by photocyclization.

The photocyclization of o-alkoxy phenyl ketones

Several o-alkoxybenzophenones and o-(benzyloxy)benzophenones and -acetophenones photocyclize to 3-hydroxy-2,3-dihydrobenzofurans. Quantum yields generally are quite high, except for o-(benzyloxy)acetophenone. The o-ethoxy and o-benzyloxy ketones form two diastereomeric products, the Z isomer being highly preferred in hydrocarbon solvents, the E isomer being formed in comparable yield in methanol or with added pyridine. The reaction involves δ-hydrogen abstraction by the ketone triplets followed by cyclization of the 1,5-biradical intermediates. The biradicals have such short lifetimes that they usually cannot be detected by flash spectroscopy or trapped by thiols. Triplet state lifetimes, determined both by steady-state quenching studies and by flash kinetics, reveal that hydrogen abstraction rate constants are quite low. Arrhenius plots for triplet decay indicate activation energies of 3-5 kcal/mol and A values of 109 for the δ-hydrogen abstraction. MMX calculations and spectroscopic data all indicate that the ketones exist primarily in conformations with the carbon α to the ether oxygen twisted well away from the carbonyl. The low observed rate constants are ascribed to even lower equilibrium populations of conformers in the geometry required for reaction in the triplet state than in the ground state. 2,6-Diacylphenyl ethers show ten times the triplet reactivity of their monoacyl equivalents. In these cases, the ether function is twisted 90° such that the target C-H bond is much closer to a carbonyl. The large solvent effects on the stereochemistry of cyclization despite short biradical lifetimes suggest that bond rotations may induce intersystem crossing of the triplet biradicals. The low cyclization quantum yield from o-(benzyloxy)acetophenone and the formation of o-benzoylacetophenone as a major side product suggest that the 1,5-biradicals partially cyclize into the benzene ring to generate spiroenol intermediates. Rate constants for quenching of the triplet ketones by 2,5-dimethyl-2,4-hexadiene were measured. The kq values are ≥5 × 109 M-1 s-1 for the o-methoxy ketones but only 1-3 × 109 for the o-benzyloxy ketones. This rare steric effect on triplet energy transfer is attributed to twisting of the benzoyl chromophores caused by steric congestion.