Dimeric Manganese-Catalyzed Hydroalkenylation of Alkynes with a Versatile Silicon-Based Directing Group.
Angew Chem Int Ed Engl
; 62(31): e202306922, 2023 Aug 01.
Article
em En
| MEDLINE
| ID: mdl-37283307
ABSTRACT
Herein, we present a manganese-catalyzed, branched-selective hydroalkenylation of terminal alkynes, under mild conditions through facile installation of a versatile silanol as a removable directing group. With an alkenyl boronic acid as the coupling partner, this reaction produces stereodefined (E,E)-1,3-dienes with high regio-, chemo- and stereoselectivity. The protocol features mild reaction conditions such as room temperature and an air atmosphere, while maintaining excellent functional group compatibility. The resulting 1,3-dienesilanol products serve as versatile building blocks, as the removal of the silanol group allows for the synthesis of both branched terminal 1,3-dienes for downstream coupling reactions, as well as stereoselective construction of linear (E,E)-1,3-dienes and (E,E,E)- or (E,E,Z)-1,3,5-trienes. In addition, a Diels-Alder cycloaddition can smoothly and selectively deliver silicon-containing pentasubstituted cyclohexene derivatives. Mechanistic investigations, in conjunction with DFT calculations, suggest a bimetallic synergistic activation model to account for the observed enhanced catalytic efficiency and good regioselectivity.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2023
Tipo de documento:
Article