Microwave-assisted epoxidation of hindered homoallylic alcohols using VO(acac)2: application to polypropionate synthesis

Torres, Gerardo; Torres, Wildeliz; Prieto, José Antonio Fernández

doi:10.1016/j.tet.2004.08.095

Cited by 22 publications

(16 citation statements)

References 41 publications

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“…The use of microwave in enhancing chemical transformations is one of the most promising non-conventional methods used in organic synthesis due to several advantages such as rapid reaction rates, solvent-free conditions and easy work-up [16]. However, few examples of application of this technique to epoxide reaction are reported in the literature: [17] in particular MW irradiation has been reported to accelerate epoxidation of α,β-unsaturated ketones and alkene [18] of allylic alcohols [19][20] and, more recently, of hindered homoallylic alcohols [21].…”

Section: Epoxidation Of Allylic Alcohols Catalyzed By Complexmentioning

confidence: 99%

Synthesis, crystal structure and application in regio- and stereoselective epoxidation of allylic alcohols of a titanium binaphthyl-bridged Schiff base complex

Soriente

Rosa

Lamberti

et al. 2005

Journal of Molecular Catalysis A: Chemical

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Section: Epoxidation Of Allylic Alcohols Catalyzed By Complexmentioning

confidence: 99%

Synthesis, crystal structure and application in regio- and stereoselective epoxidation of allylic alcohols of a titanium binaphthyl-bridged Schiff base complex

Soriente

Rosa

Lamberti

et al. 2005

Journal of Molecular Catalysis A: Chemical

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“…In this system, the C2 methyl controlled the cyclic intermediate’s conformation giving way to the anti epoxide. A microwave-assisted vanadium-catalyzed epoxidation was further developed to broaden the scope and applicability of homoallylic epoxidations [36]. Although the stereoselectivity of the epoxidation was the same as with the iodocyclization, vanadium epoxidation achieved higher yields and considerably lower reaction times for cis alkenols.…”

Section: Resultsmentioning

confidence: 99%

“…Epoxide 13 was obtained from chiral epoxide 22 using our reiterative approach previously discussed [26,36]. The resulting epoxide was cleaved with 1,3-dithiane using a modified Nakata procedure,[44] yielding 66% of diol 23 that contained the desired stereotetrad (Scheme 7).…”

Section: Resultsmentioning

confidence: 99%

Reiterative epoxide-based strategies for the synthesis of stereo-n-ads and application to polypropionate synthesis. A personal account

Cruz-Montañez

Morales-Rivera

Torres

et al. 2017

Inorganica Chimica Acta

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The enantioselective synthesis of polypropionates continues to be an attractive realm for the synthetic chemists mostly due to the challenges presented by the number of consecutive stereogenic centers contained within the aliphatic chain. Over the years, our laboratory has developed an epoxide-based three-step reiterative methodology for the construction of these targets, with the ultimate goal that the approach could be extended to the synthesis of polypropionate-containing natural products. The key steps include the diastereoselective epoxidation of allylic and homoallylic alcohols, and the regioselective cleavage of 2-methyl-3,4-epoxy alcohols. The choice of the organometallic reagent, and the cis/trans geometry of the chiral epoxide can be used to control both the relative and absolute configuration of the resulting propionate unit, allowing our approach to be applied in the synthesis of advanced fragments. Additionally, the combination of our first- and second-generation methodologies permits the incorporation of different variations at the methyl moiety.

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“…Along these lines, vanadium doped zeolites promoted the conversion of olefins into epoxides and aldehydes with the product ratio depending upon the reaction conditions [114]. Prieto reported a significant advance in the oxidation of homoallylic alcohols using discrete vanadium oxide catalysts and TBHP as the oxygen source (eqn 51) [115]. With conventional heating, the conversion from the alkene to the oxirane was sluggish (6-10 days); however, the MW assisted process required only a few hours to reach completion.…”

Section: Formation Of Epoxides and Aziridinesmentioning

confidence: 99%

Microwave Assisted Heterofunctionalization of Alkenes and Alkynes

Ide¹,

Eastlund²,

Jupe³

et al. 2008

COC

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One of the most direct and powerful ways to prepare complex organic compounds containing N, P, O, S, and related elements is the addition of the heteroatom containing group to an unsaturated fragment. Hydroelementation, Michael additions, and oxidation processes provide scientists numerous ways to effect these changes. Microwave assisted synthesis has had a dramatic effect on how synthetic chemists approach the preparation of new compounds due to dramatic increases in reaction rates. The explanation for these rapid reaction rates has not been fully addressed, and the existence of non-thermal microwave effects continues to be the subject of great debate. The blending of microwave assisted chemistry with carbon heteroatom bond forming reactions has generated a host of new and intriguing compounds.

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Microwave-assisted epoxidation of hindered homoallylic alcohols using VO(acac)2: application to polypropionate synthesis

Cited by 22 publications

References 41 publications

Synthesis, crystal structure and application in regio- and stereoselective epoxidation of allylic alcohols of a titanium binaphthyl-bridged Schiff base complex

Synthesis, crystal structure and application in regio- and stereoselective epoxidation of allylic alcohols of a titanium binaphthyl-bridged Schiff base complex

Reiterative epoxide-based strategies for the synthesis of stereo-n-ads and application to polypropionate synthesis. A personal account

Microwave Assisted Heterofunctionalization of Alkenes and Alkynes

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