39576-24-4

Upstream product

• 556-56-9 allyl iodid 
• 611-70-1 phenyl isopropyl ketone 
• 82461-21-0 2,2-dimethyl-1-phenyl-pent-4-en-1-ol 
• 106-95-6 allyl bromide 
• 10409-54-8 2-bromo-2-methyl-1-phenyl-propan-1-one 
• 1730-25-2 allylmagnesium bromide 
• 1101835-32-8 2,2-dimethyl-1-phenylpent-4-en-1-one dioxime oxalate 
• 1250849-53-6 C₁₄H₁₉NO 
• 611-69-8 rac-2-methyl-1-phenylpropan-1-ol 
• 100-52-7 benzaldehyde 
• 24850-33-7 allyltributylstanane 

Downstream Products

• 77787-31-6 4,5-dihydroxy-2,2-dimethyl-1-phenyl-pentan-1-one 
• 82461-21-0 2,2-dimethyl-1-phenyl-pent-4-en-1-ol 
• 73593-66-5 3,3-dimethyl-4-oxo-4-phenylbutanoic acid 
• 92156-71-3 2-Hydroxy-5-hydroxymethyl-3,3-dimethyl-2-phenyl-tetrahydrofuran 
• 93257-38-6 5-bromomethyl-3,3-dimethyl-2-phenyl-tetrahydro-furan-2-ol 
• 124-38-9 carbon dioxide 
• 65-85-0 benzoic acid 
• 852058-12-9 1-phenyl-2,2-dimethylpent-4-en-1-one oxime 
• 1408286-35-0 3,3-dimethyl-4-phenylpent-4-enoic acid 
• 1408286-11-2 3,3-dimethyl-4-phenylpent-4-en-1-ol 
• 1408286-13-4 4,4-dimethyl-3-phenyltetrahydro-2H-pyran 
• 1408286-12-3 2,3,3-trimethyl-2-phenyltetrahydrofuran 

Relevant academic research and scientific papers

Generation of Stable Ruthenium(IV) Ketimido Complexes by Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru?N Bond

The reaction of an oxime ester with [Ru(PPh3)3X2] proceeded smoothly at room temperature to afford a stable RuIV ketimido complex as oxidative adduct. The structure of the complex was unambiguously determined by X-ray crystallographic analysis, which showed an almost linear Ru?N?C array. The electronic properties of the nitrogen atom were estimated by DFT calculations, and the results suggested double-bond character of the Ru?N bond. Kinetic studies and consideration of the substituent effect on the oxime ester led to the proposal of a reaction mechanism involving oxidative addition, which could proceed by N,O-chelating coordination to the Ru center prior to N?O bond cleavage. The obtained Ru ketimido complex could be transformed into a ruthenacycle by C?H activation by a concerted metalation–deprotonation mechanism in dichloromethane/methanol. Ru ketimido complexes with a tethered alkyne or alkene moiety underwent chloroamination of unsaturated C?C bonds followed by C?H activation, which resulted in the formation of a ruthenacycle. Considering the LUMO of an isolated Ru ketimido complex, the chloroamination should proceed by a synchronous 1,3-dipolar cycloaddition-type mechanism. Insight into the character and reactivity of Ru ketimido complexes will be helpful for developments in the catalytic transformation of oxime esters.

NOVEL PHOTOINITIATORS MADE FROM BIFUNCTIONAL SILANE

The present invention relates to a compound of formula (I) below: in which: R1 represents, in particular, an alkylene group comprising from 1 to 6 carbon atoms; R2 and R3 are, in particular, H; n is 0, 1, 2 or 3; and Rsub

Highly Enantioselective Construction of Dihydrooxazines via Pd-Catalyzed Asymmetric Carboetherification

A straightforward synthesis of highly enantioenriched 5,6-dihydro-4H-1,2-oxazines is realized by Pd-catalyzed asymmetric carboetherification of γ,δ-alkenyl oximes with (hetero)aryl and alkenyl halides in the presence of a commercially available bisphosphine ligand. The enantioenriched products can be facilely converted to functionalized alcohols with high fidelity of chiral transfer.

Iron-catalyzed carbonylative cyclization of γ,δ-unsaturated aromatic oxime esters to functionalized pyrrolines

Herein, a new method of iron-catalyzed carbonylative cyclization of γ,δ-unsaturated aromatic oxime esters to functionalized pyrrolines has been developed. By using readily available substrates, 32 examples of functionalized pyrrolines were prepared in moderate to good yields. Notably, examples of reduction and cycloaddition reactions of the obtained product were given as well. This journal is

Additive-free radical cascade reaction of oxime esters: Synthesis of pyrroline-functionalized phenanthridines

A variety of dihydropyrrole-functionalized phenanthridines were efficiently synthesized by the metal-free, radical cascade cyclization reaction of 2-isocyanobiphenyls with γ,δ- unsaturated oxime esters. The C-N/C-C/C-C bonds were formed via the oil bath method in a one-pot procedure with broad substrate applicability. The radical process was supported by kinetic isotope effect studies and radical inhibition studies.

Copper-Catalyzed Cope-Type Hydroamination of Nonactivated Olefins toward Cyclic Nitrones: Scope, Mechanism, and Enantioselective Process Development

The catalytic synthesis of cyclic nitrones, an important type of functional molecules for both synthetic chemistry and related fields, remains underdeveloped. Herein we report the copper-catalyzed Cope-type hydroamination of oximes with pendant nonactivated olefins, which enables facile access to a series of five- and six-membered cyclic nitrones under mild conditions. In this study, heterocycle-tethered oximes were employed in the Cope-type hydroamination reaction for the first time. High enantioselectivity was achieved for carbon-tethered γ,δ-vinyl oximes to afford enantioenriched five-membered cyclic nitrones. The results of preliminary mechanistic studies indicate a mononuclear catalytic species and a unified catalytic pathway over a large temperature range.

Visible-Light-Mediated Iminyl Radical Generation from Benzyl Oxime Ether: Synthesis of Pyrroline via Hydroimination Cyclization

The treatment of an O-(4-methoxybenzyl) oxime ether bearing an olefin substituent and 1-chloroanthraquinone (1-Cl-AQN) catalyst in 2-butanone under visible-light irradiation affords pyrroline via an iminyl radical intramolecular hydroimination. Mechanistic studies indicate that iminyl radical generation mainly proceeds by hydrogen abstraction of the photocatalyst from the benzyl position of the oxime. Moreover, the hydrogen atom was identified in circulation from the benzylic position of the substrates between AQN and 2-butanone to quench the carbon radical without requiring any additional reagents.

Iminoxyl Radical-Promoted Oxycyanation and Aminocyanation of Unactivated Alkenes: Synthesis of Cyano-Featured Isoxazolines and Cyclic Nitrones

A novel and facile approach to vicinal oxycyanation and aminocyanation of internal unactivated alkenes is developed. This method utilizes the dichotomous reactivity of iminoxyl radical derived from the initiation of β,γ- and γ,δ-unsaturated ketoximes to provide the general difunctionalization of internal alkenes using tert-butyl hydroperoxide (TBHP) as the environmentally friendly oxidant, CuCN as the commercially available cyanating reagent, and pentamethyldiethylenetriamine (PMDETA) as the ligand. By using this protocol, a series of useful cyano-featured isoxazolines and cyclic nitrones were efficiently prepared.

An Umpolung Approach to Alkene Carboamination: Palladium Catalyzed 1,2-Amino-Acylation, -Carboxylation, -Arylation, -Vinylation, and -Alkynylation

Conventional approaches to Pd-catalyzed alkene 1,2-carboamination rely upon the combination of a nucleophilic nitrogen-based component and an internal C-based or external oxidant. In this study, we outline an umpolung approach, which is triggered by oxidative initiation at an electrophilic N-based component and employs "standard" organometallic nucleophiles to introduce the new carbon-based fragment. Specifically, oxidative addition of a Pd(0)-catalyst into the N-O bond of O-pentafluorobenzoyl oxime esters generates imino-Pd(II) intermediates, which undergo 5-exo cyclization with sterically diverse alkenes. The resultant alkyl-Pd(II) intermediates are intercepted by organometallic nucleophiles or alcohols, under carbonylative or noncarbonylative conditions, to provide 1,2-carboamination products. This approach provides, for the first time, a unified strategy for achieving alkene 1,2-amino-acylation, -carboxylation, -arylation, -vinylation, and -alkynylation. For carbonylative processes, orchestrated protodecarboxylation of the pentafluorobenzoate leaving group underpins reaction efficiency. This process is likely a key feature in related Narasaka-Heck cyclizations and accounts for the efficacy of O-pentafluorobenzoyl oxime esters in aza-Heck reactions of this type. (Chemical Equation Presented).

Copper-catalyzed cyclization and azidation of γ,δ-unsaturated ketone O-benzoyl oximes

An intramolecular imination/azidation sequence has been realized through the tetrakis(acetonitrile)copper(I) hexafluorophophate [Cu(CH3CN)4PF6]-catalyzed reaction of γ,δ-unsaturated ketone O-benzoyl oximes with trimethylsi