Efficient access to polysubstituted tetrahydrofurans by electrophilic cyclization of vinylsilyl alcohols

Barbero, Asunción; Barbero, Héctor; González‐Ortega, Alfonso; Pulido, Francisco J.; Val, Patricia; Diez‐Varga, Alberto; Morán, Joaquı́n R.

doi:10.1039/c5ra06640a

Cited by 6 publications

(2 citation statements)

References 28 publications

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“…Unless otherwise noted, all reagents were obtained from commercial suppliers as reagent grade and used without further purification. Compounds 1 - 3 were prepared according to literature [ 20 ].…”

Section: Methodsmentioning

confidence: 99%

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

Díez-Poza

Barbero

2021

Molecules

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The regioselective ring opening of epoxy alcohols is an effective method for the synthesis of different types of oxacycles. The 5-exo opening being preferred vs. the 6-endo mode, according to Baldwin rules, the use of silyl-substituted oxiranes has been reported as a possible method to favor the 6-endo cyclization. However, there is a need for a detailed study on the different factors (structural factors, catalyst nature or conditions) that influence this process. In this paper, the acid-catalyzed cyclization of epoxysilyl alcohols was studied, focusing on the effect of substituents and reaction conditions on the outcome of the process. Two types of heterocycles (tetrahydrofurans or tetrahydropyrans) were selectively obtained depending on the structure of the initial epoxysilyl alcohol. Interestingly, cyclization of hindered epoxysilyl alcohols mainly proceeds through an unexpected side reaction, which implies a previous isomerization to an aldehyde. A mechanistic proposal for the formation of the different products is presented.

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Section: Methodsmentioning

confidence: 99%

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

Díez-Poza

Barbero

2021

Molecules

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“…For many years our research group has been devoted to exploring new synthetic approaches to the synthesis of carbo- [ 15 , 16 , 17 ] and heterocycles [ 18 , 19 ] using the chemistry of organosilanes. Lately, Hosomi [ 20 , 21 ] and our group [ 22 , 23 ] have reported an efficient synthesis of tetrahydrofurans by intramolecular hydroalkoxylation reaction of vinyl or allylsilanes. In this paper, we report the extension of this work to the stereoselective synthesis of polysubstituted tetrahydropyrans by the acid-mediated cyclization of activated vinylsilyl alcohols.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Polysubstituted Tetrahydropyrans by Stereoselective Hydroalkoxylation of Silyl Alkenols: En Route to Tetrahydropyranyl Marine Analogues

Díez-Poza¹,

Val²,

Pulido³

et al. 2018

Marine Drugs

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Tetrahydropyrans are abundantly found in marine natural products. The interesting biological properties of these compounds and their analogues make necessary the development of convenient procedures for their synthesis. In this paper, an atom economy access to tetrahydropyrans by intramolecular acid-mediated cyclization of silylated alkenols is described. p-TsOH has shown to be an efficient reagent to yield highly substituted tetrahydropyrans. Moreover, excellent diastereoselectivities are obtained both for unsubstituted and alkylsubstituted vinylsilyl alcohols. The methodology herein developed may potentially be applied to the synthesis of marine drugs derivatives.

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Stereoselective Synthesis of Polysubstituted Tetrahydropyrans by Brønsted Acid‐Mediated Hydroxyalkoxylation of Silylated Alkenols

Díez‐Poza,

Val,

López

et al. 2024

Asian J Org Chem

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A convenient route for the preparation of tetrahydropyran (THP) derivatives with a quaternary and tertiary vicinal stereocenters is reported. The atom economy acid‐catalyzed cyclization of allylsilyl alcohols provided polysubstituted tetrahydropyrans in good yields and excellent diastereoselectivities (>95:5). In comparison with the traditional oxymercuration procedure, this approach resulted to be more efficient in both yield and stereocontrol.

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Efficient access to polysubstituted tetrahydrofurans by electrophilic cyclization of vinylsilyl alcohols

Cited by 6 publications

References 28 publications

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

Synthesis of Polysubstituted Tetrahydropyrans by Stereoselective Hydroalkoxylation of Silyl Alkenols: En Route to Tetrahydropyranyl Marine Analogues

Stereoselective Synthesis of Polysubstituted Tetrahydropyrans by Brønsted Acid‐Mediated Hydroxyalkoxylation of Silylated Alkenols

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