Regio- and Enantioselective Baeyer–Villiger Oxidation: Kinetic Resolution of Racemic 2-Substituted Cyclopentanones

Zhou, Lin; Liu, Xiaohua; Ji, Jie; Zhang, Yuheng; Wu, Wangbin; Liu, Yangbin; Lin, Lili; Feng, Xiaoming

doi:10.1021/ol501737a

Cited by 37 publications

(22 citation statements)

References 70 publications

(12 reference statements)

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“…The resultsw ere similar,a lthough the process was markedly faster at shorter wavelengths.I rradiation of 1 was performed at l max = 300 and 254 nm, in am ultilamp photoreactor. The course of the reaction was followed by 1 HNMR spectroscopy.A fter purification by column chromatography,i mine 2 [16] and lactone 3 [17] were separated from the reaction crude as the sole photoproducts( Scheme 2). The 1 Ha nd 13 CNMR spectra of isolated 2 matched with those of ac ommerciallya vailable sample, whereas, in the case of 3,t hey were compared with data reported in the literature.…”

Section: Resultsmentioning

confidence: 99%

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A New Pathway for Protein Haptenation by β‐Lactams

Pérez‐Ruiz

Lence

Andreu

et al. 2017

Chemistry A European J

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The covalent binding of β-lactams to proteins upon photochemical activation has been demonstrated by using an integrated approach that combines photochemical, proteomic and computational studies, selecting human serum albumin (HSA) as a target protein and ezetimibe (1) as a probe. The results have revealed a novel protein haptenation pathway for this family of drugs that is an alternative to the known nucleophilic ring opening of β-lactams by the free amino group of lysine residues. Thus, photochemical ring splitting of the β-lactam ring, following a formal retro-Staudinger reaction, gives a highly reactive ketene intermediate that is trapped by the neighbouring lysine residues, leading to an amide adduct. For the investigated 1/HSA system, covalent modification of residues Lys414 and Lys525, which are located in sub-domains IIIA and IIIB, respectively, occurs. The observed photobinding may constitute the key step in the sequence of events leading to photoallergy. Docking and molecular dynamics simulation studies provide an insight into the molecular basis of the selectivity of 1 for these HSA sub-domains and the covalent modification mechanism. Computational studies also reveal positive cooperative binding of sub-domain IIIB that explains the experimentally observed modification of Lys414, which is located in a barely accessible pocket (sub-domain IIIA).

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Section: Resultsmentioning

confidence: 99%

“…The 1 Ha nd 13 CNMR spectra of isolated 2 matched with those of ac ommerciallya vailable sample, whereas, in the case of 3,t hey were compared with data reported in the literature. [17] Thec orresponding 1 Ha nd 13 CNMR spectra are shown in FiguresS1-S4 in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

A New Pathway for Protein Haptenation by β‐Lactams

Pérez‐Ruiz

Lence

Andreu

et al. 2017

Chemistry A European J

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“…Based on the above success, they further developed a highly regio‐ and enantioselective B‐V oxidation of racemic 2‐substituted cyclopentanones using the N , N′ ‐dioxide 24 ‐derived Sc(III) complex catalyst (Scheme ) . A strong additive effect was observed in this reaction, when 4 Å MS and Al(OEt) 3 were used, the asymmetric B‐V oxidation of 2 could afford the desired δ‐lactones in 87–98% enantioselectivities and moderate to good regioselectivities.…”

Section: Kinetic Resolutionmentioning

confidence: 99%

Advances in Chemocatalytic Asymmetric Baeyer–Villiger Oxidations

et al. 2020

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Baeyer–Villiger oxidations, first reported by Adolf von Baeyer and Victor Villiger 120 years ago, are highly efficient methodologies for the syntheses of esters or lactones from ketones. The asymmetric Baeyer–Villiger oxidations using racemic, prochiral and meso‐cyclic ketones allow a rapid access to chiral lactones, which are valuable intermediates for the subsequent synthesis of bioactive compounds and natural products. The current review provides a summary on the advances in chemocatalytic enantioselective B‐V oxidations. The latest achievements in this field and their applications are presented.

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“…In the new born era, oxidation reactions play a vital role in many fields that benefit the chemical industries for the manufacture of high tonnage commodities, high‐value fine chemicals, chemical intermediates and the pharmaceuticals . For instance, Baeyer–Villiger (BV) reaction is a significant oxidation process, providing a straight corridor to oxidize ketones to lactones or esters by organic peracids; and they are hefty industrial intermediates, with significance on the production of high valuable fine chemicals (e.g., steroids, antibiotics, antiviral and antiproliferative agents) . Consequently, the development of efficient and sustainable preparative methods to access these related skeletons are of enormous importance in synthetic organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Baeyer‐Villiger oxidation of cyclopentanone over zeolite Y entrapped transition metal‐Schiff base complexes

Modi

Solanki

Vithalani

et al. 2017

Applied Organom Chemis

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Transition metal [M = VO (IV) and/or Cu (II)] complexes with Schiff base ligand, (Z)-2-((2-hydroxybenzylideneamino)phenol (H 2 L) have been entrapped in the super cages of zeolite-Y by Flexible Ligand Method. Synthesized materials have been characterized by preferential physico-chemical techniques such as inductively coupled plasma optical emission spectroscopy (ICP-OES), elemental analyses (CHN), fourier transmission infrared spectroscopy (FTIR), electronic and UVreflectance spectra, Brunauer-Emmett-Teller (BET) surface area measurements, scanning electron micrographs (SEMs), X-ray diffraction patterns (XRD) and thermogravimetric analysis (TGA). The catalytic competence of zeolite-Y entrapped transition metal complexes was examined in Baeyer-Villiger (BV) oxidation of cyclopentanone using 30% H 2 O 2 as an oxidant beside neat complexes to check the aptitude of heterogeneous catalysis over the homogeneous system. The effect of experimental variables such as mole ratio of substrate to an oxidant, amount of catalyst, reaction time, varying oxidants and solvents on the conversion of cyclopentanone was also tested. Under the optimized reaction conditions, one of the zeolite-Y entrapped transition metal complex viz. [VO(L)H 2 O]-Y [where L = (Z)-2-((2-hydroxybenzylideneamino)phenol] was found to be a potential contender by providing 80.22% conversion of cyclopentanone (TON: 10479.42), and the selectivity towards δ-valerolactone was 83.56%. KEYWORDS Baeyer-Villiger oxidation of cyclopentanone, flexible ligand method, heterogeneous catalysts, zeolite-Y entrapped transition metal complexes

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Regio- and Enantioselective Baeyer–Villiger Oxidation: Kinetic Resolution of Racemic 2-Substituted Cyclopentanones

Cited by 37 publications

References 70 publications

A New Pathway for Protein Haptenation by β‐Lactams

A New Pathway for Protein Haptenation by β‐Lactams

Advances in Chemocatalytic Asymmetric Baeyer–Villiger Oxidations

Baeyer‐Villiger oxidation of cyclopentanone over zeolite Y entrapped transition metal‐Schiff base complexes

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