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331.
A bifunctional catalyst system composed of (S)-prolinamide (2a), titanium(IV) isopropoxide, and phenolic N-oxide (3f) exhibited high catalytic efficiency in the enantioselective cyanosilylation of ketones. In the presence of 2.5 mol % catalyst, a variety of aromatic and aliphatic ketones were converted into the corresponding tertiary cyanohydrin O-TMS ethers in excellent yields (up to 96%) and high enantioselectivities (up to 96% ee). A proposed catalytic cycle was illustrated to explain the origin of the asymmetric induction. 相似文献
332.
Douglas A. Engel 《Tetrahedron》2008,64(29):6988-6996
In principle, the most efficient and atom-economical means of converting an aldehyde or ketone into the homologated α,β-unsaturated ester is through addition/rearrangement sequences involving acetylenic π-bonds (Scheme 1). Implementation of such a strategy for the synthesis of α,β-unsaturated esters is presented: addition of ethoxyacetylene followed by scandium(III) triflate-catalyzed Meyer-Schuster rearrangement reaction. Stereoselectivities range from good to excellent in the formation of disubstituted α,β-unsaturated esters from aldehydes (Table 3). The two-stage olefination of even the most hindered ketones proceeds with near perfect efficiency (Table 4). 相似文献
333.
Peng-Ying Jiang Dr. San Wu Dr. Guan-Jun Wang Dr. Shao-Hua Xiang Prof. Dr. Bin Tan 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309272
QUINAPs have emerged as a pivotal class of axially chiral compounds with remarkable features in the stereoinduction of diverse enantioselective transformations. However, the confined substrate range and extravagant price still pose challenges, limiting their broader utilization. Herein, we describe the first atroposelective oxidation of an N atom using a chiral ketone catalyst, allowing the kinetic resolution of QUINAPOs to give both the unreacted substrates and their corresponding N-oxides with excellent enantioselectivity. Importantly, the enantioenriched products can be readily converted into the QUINAP targets without any loss of stereochemical integrity. Mechanistic investigations indicate that a dioxirane, generated through the oxidation of the ketone with oxone, acts as the active catalytic species. Furthermore, we have successfully extended this catalytic system to the kinetic resolution of QUINOLs and the dynamic kinetic transformation of pyridine analogues of QUINAPO possessing a labile stereogenic axis. The practicality of the developed protocol is further demonstrated by the successful application of QUINAPO N-oxide as a Lewis base catalyst in a series of enantioselective transformations. 相似文献
334.
Doménech-Carbó MT Yusá-Marco DJ Bitossi G Silva MF Mas-Barberá X Osete-Cortina L 《Analytical and bioanalytical chemistry》2008,391(4):1351-1359
This paper presents a study of thin films of the commercial ketone resins Laropal K80, Keton N and MS2A, attempting to reproduce the pictorial layers and protective finishes commonly present in contemporary paintings. Chemical and morphological changes due to the degradation effect of environmental agents have been specially considered. For this purpose, three different accelerated ageing processes were applied to a series of specimens prepared from the studied commercial products: thermal, UV light and ageing in an SO(2)-polluted chamber. Spectroscopic techniques such as FTIR spectroscopy and UV-Vis spectrophotometry were applied in combination with microscopic examination techniques, namely, AFM and scanning electron microscopy energy dispersive X-ray microanalysis (SEM-EDX). Chemical changes due to UV light and thermal ageing are in good agreement with those previously reported in the literature. Bleaching exhibited by the three commercial products after exposure to a SO(2)-saturated atmosphere has been related to the diffusion of SO(2)-rich water vapour into the film. This effect was particularly strong in the MS2A resin due to the higher content of hydroxyl groups in this product. 相似文献
335.
α-Alkylation of ketones with styrene derivatives was developed using a mesitylcopper-dppp complex as a soft Brønsted base catalyst. No waste derived from the alkylating reagent was produced in this catalytic alkylation reaction. The bisphosphine ligand structure, as well as the reaction solvent, had profound effects on catalyst activity. The reaction proceeded under mild conditions from a range of ketones and styrene derivatives. The present catalysis is especially useful for the selective mono-alkylation of ketones. 相似文献
336.
337.
Olivier Jacquet 《Tetrahedron》2010,66(1):222-226
Stereochemically-biased bicyclic allylic acetates endo- and exo-1 were shown as being allyl donors for Pd-catalyzed carbonyl allylation using stoichiometric quantities of samarium diodide. Cyclopentenyl acetate and bicyclic derivatives 1 react with cyclic ketones in the presence of SmI2 without requirement of palladium catalysis. Use of enantiomerically enriched substrate suggests that the reaction goes through a π-allyl samarium complex. However, this reactivity appears to be restricted to strained cyclopentenyl acetates since other linear and cyclic allylic acetates do not give the carbonyl allylation product. 相似文献
338.
Aliphatic ketones were reduced to the corresponding secondary alcohols by using anti-1,3-diol and a catalytic amount of 2,4-dinitrobenzenesulfonic acid (DNBSA) in benzene at reflux. Addition of 1-octanethiol in that media improved the efficiency of the reduction. Asymmetric reduction of aliphatic ketones was performed by using chiral anti-pentane-2,4-diol, and highly asymmetric induction (up to >99% ee) was observed in the reduction of tert-alkyl ketones. Asymmetric reduction of acyl silanes using chiral anti-pentane-2,4-diol and DNBSA proceeded efficiently in the absence of octanethiol and the corresponding α-silyl alcohols were obtained in high yields with high ees. 相似文献
339.
340.
Nuwayo Eric Munyaneza Carlos Posada Zhen Xu Vincenzo De Altin Popiolek Griffin Paddock Charles McKee Dr. Guoliang Liu 《Angewandte Chemie (International ed. in English)》2023,62(36):e202307042
Polystyrene (PS) is one of the least recycled large-volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of “degradation-upcycling” to synthesize a library of high-value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value-added chemicals. 相似文献