Intra- and intermolecular alkylation of N,O-acetals and π-activated alcohols catalyzed by in situ generated acid.
Identifieur interne : 000337 ( Main/Exploration ); précédent : 000336; suivant : 000338Intra- and intermolecular alkylation of N,O-acetals and π-activated alcohols catalyzed by in situ generated acid.
Auteurs : Mélanie Hamon [France] ; Niall Dickinson ; Alice Devineau ; David Bolien ; Marie-José Tranchant ; Catherine Taillier ; Ivan Jabin ; David C. Harrowven ; Richard J. Whitby ; A. Ganesan ; Vincent DallaSource :
- The Journal of organic chemistry [ 1520-6904 ] ; 2014.
English descriptors
- KwdEn :
- MESH :
- chemical , analogs & derivatives : Ethane.
- chemical , chemistry : Acetals, Alcohols, Ethane, Hydrocarbons, Chlorinated, Indicators and Reagents, Solvents.
- Alkylation, Catalysis, Microwaves, Molecular Structure.
Abstract
Intramolecular and intermolecular alkylations of carbocation precursors of limited ionization ability, principally N,O-acetals, without the use of an exogenous reagent have been developed. The reactions are carried out in 1,1,2,2-tetrachloroethane (TCE) and take advantage of the ability of this solvent to continuously release small amounts of HCl by thermolytic elimination. A study of the reaction led to several improved protocols such as (1) preheated TCE, (2) microwave-assisted reactions, and (3) flow or sealed-tube conditions, which allow significant reaction rate enhancements and made possible some challenging reactions such as the α-amidoalkylation of ketones. Studies using flow chemistry confirmed not only that very low concentrations of HCl generated from the solvent were responsible for the reactivity but also that TCE had additional beneficial properties in comparison to other chlorinated solvents such as dichloroethane. The method can easily be extended to the alkylation using proelectrophiles such as π-activated alcohols, which are normally unreactive toward HCl catalysis. This work represents the first successful use of HCl, the simplest strong Brønsted acid, as an efficient alkylation catalyst.
DOI: 10.1021/jo4015886
PubMed: 24533649
Affiliations:
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Le document en format XML
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The reactions are carried out in 1,1,2,2-tetrachloroethane (TCE) and take advantage of the ability of this solvent to continuously release small amounts of HCl by thermolytic elimination. A study of the reaction led to several improved protocols such as (1) preheated TCE, (2) microwave-assisted reactions, and (3) flow or sealed-tube conditions, which allow significant reaction rate enhancements and made possible some challenging reactions such as the α-amidoalkylation of ketones. Studies using flow chemistry confirmed not only that very low concentrations of HCl generated from the solvent were responsible for the reactivity but also that TCE had additional beneficial properties in comparison to other chlorinated solvents such as dichloroethane. The method can easily be extended to the alkylation using proelectrophiles such as π-activated alcohols, which are normally unreactive toward HCl catalysis. This work represents the first successful use of HCl, the simplest strong Brønsted acid, as an efficient alkylation catalyst.</div></front></TEI><affiliations><list><country><li>France</li></country><region><li>Haute-Normandie</li><li>Région Normandie</li></region><settlement><li>Le Havre</li></settlement></list><tree><noCountry><name sortKey="Bolien, David" sort="Bolien, David" uniqKey="Bolien D" first="David" last="Bolien">David Bolien</name><name sortKey="Dalla, Vincent" sort="Dalla, Vincent" uniqKey="Dalla V" first="Vincent" last="Dalla">Vincent Dalla</name><name sortKey="Devineau, Alice" sort="Devineau, Alice" uniqKey="Devineau A" first="Alice" last="Devineau">Alice Devineau</name><name sortKey="Dickinson, Niall" sort="Dickinson, Niall" uniqKey="Dickinson N" first="Niall" last="Dickinson">Niall Dickinson</name><name sortKey="Ganesan, A" sort="Ganesan, A" uniqKey="Ganesan A" first="A" last="Ganesan">A. Ganesan</name><name sortKey="Harrowven, David C" sort="Harrowven, David C" uniqKey="Harrowven D" first="David C" last="Harrowven">David C. Harrowven</name><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name><name sortKey="Taillier, Catherine" sort="Taillier, Catherine" uniqKey="Taillier C" first="Catherine" last="Taillier">Catherine Taillier</name><name sortKey="Tranchant, Marie Jose" sort="Tranchant, Marie Jose" uniqKey="Tranchant M" first="Marie-José" last="Tranchant">Marie-José Tranchant</name><name sortKey="Whitby, Richard J" sort="Whitby, Richard J" uniqKey="Whitby R" first="Richard J" last="Whitby">Richard J. Whitby</name></noCountry><country name="France"><region name="Région Normandie"><name sortKey="Hamon, Melanie" sort="Hamon, Melanie" uniqKey="Hamon M" first="Mélanie" last="Hamon">Mélanie Hamon</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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