Superacid-Promoted Synthesis of CF3-Indenes Using Brominated CF3-Enonesстатья
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Дата последнего поиска статьи во внешних источниках: 23 ноября 2017 г.
Авторы:
Iakovenko Roman O. ,
Kazakova Anna N.,
Boyarskaya Irina A. ,
Gurzhiy Vladislav V. ,
Avdontceva Margarita S. ,
Panikorovsky Taras L. ,
Muzalevskiy Vasiliy M. ,
Nenajdenko Valentine G. ,
Vasilyev Aleksander V.
Журнал:
European Journal of Organic Chemistry
Год издания:
2017
Издательство:
John Wiley & Sons Ltd.
Местоположение издательства:
United Kingdom
Первая страница:
5632
Последняя страница:
5643
DOI:
10.1002/ejoc.201701085
Аннотация:
The reactions of 3-bromo- and 3,4-dibromo-CF3-enones
with superacids were studied. Protonation of these CF3-
enones with FSO3H resulted in the formation of cationic species
that subsequently cyclized at –60 °C to give the corresponding
mono- and dibromoindenols in up to 98 % yield. Protonation
of the indenol products at room temperature with triflic acid
(CF3SO3H) provided highly electrophilic trifluoromethylated ind-
Introduction
Organofluorine compounds are widely used in chemistry,
biology, medicine, and other areas due to the unique properties
that arise from the incorporation of a fluorine atom or a fluorinated
fragment into a molecule.[1,2] The presence of a fluorinated
fragment in a structure can significantly change the chemical,
physical, and biological properties of a compound. The building-
block approach is one of the most attractive methods for
the construction of fluorinated compounds; it gives access to
structures containing a fluorinated fragment attached to the
desired atom. CF3-enones are a very useful type of fluorinated
building blocks that have a wide range of synthetic applications.
Recently, a family of mono- and dibrominated 1,1,1-
trifluorobut-3-en-2-ones was found to have unique chemical
properties due to the presence in their structure of several electrophilic
sites. These trifluoromethylated compounds are able
to trigger domino reactions with various oxygen or nitrogen
[a] Department of Organic Chemistry, Institute of Chemistry,
Saint Petersburg State University,
Universitetskaya nab. 7/9, Saint Petersburg 199034, Russia
E-mail: a.vasilyev@spbu.ru
http://chem.spbu.ru/research/nauchnye-gruppy/237-scientific-activities/
research-groups/951-nauchnaya-gruppa-professora-a-v-vasileva.html
[b] Center for X-ray Diffraction Studies Research Park,
St. Petersburg State University,
Universitetskiy pr. 26, Saint Petersburg, Petrodvoretz 198504, Russia
[c] Department of Chemistry, Lomonosov Moscow State University,
Vorobievy Gory 1, Moscow 119899, Russia
E-mail: nen@acylium.chem.msu.ru
http://www.chem.msu.ru/eng/welcome.html
[d] Department of Chemistry,
Saint Petersburg State Forest Technical University,
Institutsky per. 5, Saint Petersburg 194021, Russia
E-mail: aleksvasil@mail.ru
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201701085.
Eur. J. Org. Chem. 2017, 5632–5643 5632 © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
enyl cations. Subsequent reaction with various arenes gave access
to 1-CF3-substituted indenes in up to 84 % yields. DFT calculations
were carried out to obtain data about the electronic
structure and electrophilicity of the cationic intermediates. The
mechanisms of these multistep transformations of highly electrophilic
cationic intermediates are discussed.
Добавил в систему:
Ненайденко Валентин Георгиевич