Synthesis of Alkyl Hydroperoxides via Alkylation of <i>gem</i>-Dihydroperoxides

Kyasa, ShivaKumar; Puffer, Benjamin W.; Dussault, Patrick H.

doi:10.1021/jo4001564

Cited by 32 publications

(32 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The question of chemoselective generation of an organolithium nucleophile was initially investigated using a dialkyl peroxide ( 1 ) derived from reaction of t -butyl hydroperoxide with dihydrogeraniol methanesulfonate. 9 Consistent with previous observations, 3a reaction of 1 with n -BuLi proceeded readily to furnish butyl ether 2 (eq 1). Repeating this reaction in the presence of a slight excess of allyl tributylstannane resulted in predominant formation of the allyl ether ( 3 ), demonstrating that Li/heteroatom exchange proceeds much more rapidly than C–O bond formation.…”

supporting

confidence: 89%

Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides

2014

Self Cite

View full text Add to dashboard Cite

show abstract

supporting

confidence: 89%

Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides

2014

Self Cite

View full text Add to dashboard Cite

show abstract

“…Table 1 illustrates preparation of substrates. Base-promoted alkylation of hydroperoxides with primary and secondary triflates 22 provided good yields of t -butyl/alkyl peroxides ( 8a – 11a ), monoperoxyacetals ( 8c , 23 8b – 10b , 12b , 13b ( 24 )), and a 2-methoxyethyl peroxide ( 9e ). Tetrahydropyranyl monoperoxyacetals ( 14b , 15b ) were also prepared through acetalization of hydroperoxides with dihydropyran.…”

Section: Resultsmentioning

confidence: 99%

“…[123369-58-4] was prepared by alkylation of a 1,1-dihydroperoxycyclodecane, followed by hydrolysis of the resulting bisperoxyacetal. 22 …”

Section: Methodsmentioning

confidence: 99%

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

et al. 2015

Self Cite

View full text Add to dashboard Cite

Although transfer of electrophilic alkoxyl (“RO+”) from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O–O bond.

show abstract

“… 2013 ), benzyl hydroperoxide ( 8 ) (Kyasa et al. 2013 ), 2,3-dihydroxy-1-(4-hydroxy-3-methoxyphenyl)-propan-1-one ( 9 ) (Baderschneider & Winterhalter 2001 ), octadeca-9 Z ,12 Z -dienoic acid ( 10 ) (Butovich & Lukyanovaon 2008 ), 9,12,13-trihydroxyoctadeca-10 E -enoic acid ( 11 ) (Oueslati et al. 2006 ), 9,12,13-trihydroxyoctadeca-10 E ,15 Z -dienoic acid ( 12 ) (Oueslati et al.…”

Section: Resultsmentioning

confidence: 99%

Antibacterial activities of chemical constituents from the aerial parts of Hedyotis pilulifera

Nguyen

et al. 2017

Pharmaceutical Biology

View full text Add to dashboard Cite

Context:Hedyotis pilulifera (Pit.) T.N. Ninh (Rubiaceae) has been used in Vietnamese ethnomedicine; the methanol extract exhibited antibacterial activity in our preliminary screening.Objectives: In this study, compounds from H. pilulifera were isolated and their antibacterial activity in vitro was evaluated.Materials and methods: The aerial parts of H. pilulifera (1.4 kg) were extracted with MeOH, suspended in water and ethyl acetate extract was chromatographed on a silica gel column. The structures of isolated compounds were elucidated by the combination analyses of spectroscopy including 1D-, 2D-NMR, HRMS and in comparison with the reported NMR data in the literature. All isolated compounds were evaluated for inhibitory effect using the microdilution method toward Staphylococcus aureus, Bacillus subtilis and Mycobacterium smegmatis, and MIC values were determined.Results: Twenty compounds were isolated, including five triterpenoids, two steroids, two aromatic compounds, three fatty acids, one quinone derivative, one lignan glycoside, one ceramide and five glycolipids. Among these, oleanolic acid showed significant antibacterial activity against M. smegmatis with the MIC value of 2.5 μg/mL. Remarkably, rotungenic acid showed strong activity against S. aureus, B. subtilis, M. smegmatis with MIC values of 2.5, 2.5 and 1.25 μg/mL, respectively. Rotundic acid exhibited significant antibacterial activity against B. subtilis with the MIC value of 5 μg/mL. To the best of our knowledge, the antibacterial activity of rotungenic acid, stigmast-4-ene-3,6-dione and (2S,3S,4R,2′R)-2-(2′-hydroxytetracosanoylamino) octadecane-1,3,4-triol was reported for the first time.Conclusions: Oleanolic acid, rotungenic acid, and rotundic acid were considered to be useful for developing new antimicrobial therapeutic agents for human.

show abstract

Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

Abstract: Two-fold alkylation of 1,1-dihydroperoxides, followed by hydrolysis of the resulting bisperoxyacetals, provides a convenient method for synthesis of primary and secondary alkyl hydroperoxides.

Cited by 32 publications

References 30 publications

Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides

Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

Antibacterial activities of chemical constituents from the aerial parts of Hedyotis pilulifera

Contact Info

Product

Resources

About