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Catalytic enantioselective synthesis of perfluoroalkyl-substituted β-lactones via a concerted asynchronous [2 + 2] cycloaddition : a synthetic and computational study
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Barrios Antúnez, Diego-Javier, Greenhalgh, Mark D., Brueckner, Alexander C., Walden, Daniel M., Elías-Rodríguez, Pilar, Roberts, Patrick, Young, Benjamin G., West, Thomas H., Slawin, Alexandra M. Z., Ha-Yeon Cheong, Paul and Smith, Andrew D. (2019) Catalytic enantioselective synthesis of perfluoroalkyl-substituted β-lactones via a concerted asynchronous [2 + 2] cycloaddition : a synthetic and computational study. Chemical Science, 10 (24). pp. 6162-6173. doi:10.1039/C9SC00390H ISSN 2041-6520.
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Official URL: http://dx.doi.org/10.1039/C9SC00390H
Abstract
The enantioselective preparation of a range of perfluoroalkyl-substituted β-lactones through an isothiourea (HyperBTM) catalysed reaction using symmetric anhydrides as ammonium enolate precursors and perfluoroalkylketones (RF = CF3, C2F5, C4F9) is reported. Following optimisation, high diastereo- and enantioselectivity was observed for β-lactone formation using C2F5- and C4F9-substituted ketones at room temperature (26 examples, up to >95 : 5 dr and >99 : 1 er), whilst −78 °C was necessary for optimal dr and er with CF3-substituted ketones (11 examples, up to >95 : 5 dr and >99 : 1 er). Derivatisation of the β-lactones through ring-opening, as well as a two-step conversion to give perfluoroalkyl-substituted oxetanes, is demonstrated without loss of stereochemical integrity. Density functional theory computations, alongside 13C natural abundance KIE studies, have been used to probe the reaction mechanism with a concerted asynchronous [2 + 2]-cycloaddition pathway favoured over a stepwise aldol–lactonisation process.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
Library of Congress Subject Headings (LCSH): | Lactones, Lactones -- Synthesis , Ring formation (Chemistry) , Anhydrides, Density functionals | ||||||||||||
Journal or Publication Title: | Chemical Science | ||||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||||
ISSN: | 2041-6520 | ||||||||||||
Official Date: | 28 June 2019 | ||||||||||||
Dates: |
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Volume: | 10 | ||||||||||||
Number: | 24 | ||||||||||||
Page Range: | pp. 6162-6173 | ||||||||||||
DOI: | 10.1039/C9SC00390H | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||
Date of first compliant deposit: | 29 April 2020 | ||||||||||||
Date of first compliant Open Access: | 29 April 2020 | ||||||||||||
RIOXX Funder/Project Grant: |
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