Decatungstate-Catalyzed Hydrosilylation of α-Trifluoromethylalkenes for Construction of α-Trifluoromethyl-β-silanes
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 18, 2025
The
hydrosilylation
of
alkenes
is
a
pivotal
transformation
for
the
synthesis
organosilanes;
however,
fluorine-containing
limited
due
to
facile
β-fluoride
elimination.
Herein,
by
employing
direct
hydrogen
atom
transfer
(HAT)
catalyst,
tetrabutylammonium
decatungstate
(TBADT),
and
using
disulfide
as
co-catalyst,
we
have
successfully
developed
mild
photocatalytic
α-trifluoromethylalkenes
α-trifluoromethyl-β-silanes.
Our
method
features
conditions,
good
regioselectivity,
compatibility.
elimination
was
fully
inhibited.
A
radical
mechanism
proposed
based
on
preliminary
results.
Язык: Английский
Transition‐Metal‐Free Carbonyl Reduction and Hydrodefluorination of β‐Trifluoromethyl Enones with Hydrosilanes: Synthesis of gem‐Difluorovinyl Alcohols
Peng‐Yuan Zhang,
Ya‐Fei Hu,
Jia‐Hao Chu
и другие.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(23)
Опубликована: Апрель 20, 2024
Abstract
A
tandem
carbonyl
reduction
and
hydrodefluorination
of
β‐trifluoromethyl
enones
with
hydrosilanes
under
transition‐metal‐free
conditions
was
developed
for
the
synthesis
a
variety
valuable
gem
‐difluorovinyl
alcohols.
The
hydrosilane
could
act
as
both
reductive
agent
C(sp
3
)‐F
bond‐breaking
promoter
mild
reaction
conditions.
Synthetically
useful
organofluorides,
such
‐fluorophosphine
alkene,
ketone,
fluorinated
dihydrofuran
derivatives
be
readily
constructed
by
further
transformations
obtained
Moreover,
method
features
conditions,
operational
simplicity,
excellent
functional
group
tolerance,
scalability.
Язык: Английский
Creation of a Chiral All-Carbon Quaternary Center Induced by CF3 and CH3 Substituents via Cu-Catalyzed Asymmetric Conjugate Addition
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5312 - 5317
Опубликована: Июнь 13, 2024
Cu-catalyzed
asymmetric
construction
of
a
chiral
quaternary
center
bearing
CH3
and
CF3
groups
was
achieved
with
high
to
excellent
enantioselectivity
using
our
originally
developed
ligands.
The
conjugate
addition
Me3Al
β-CF3-substituted
enones
unsaturated
ketoesters
proceeded
efficiently.
use
gives
optically
active
furanones
in
yields
enantioselectivities.
perfluoroalkyl-substituted
enone
does
not
seem
be
favorable
the
present
reaction.
Язык: Английский
Ruthenium-Catalyzed Meta-Selective Trifluoroisopropylation of Arenes
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8601 - 8609
Опубликована: Июнь 5, 2024
This
work
reports
the
mild
and
efficient
Ru-catalyzed
trifluoroisopropylation
of
arenes
using
2-bromo-1,1,1-trifluoropropane.
Various
bioactive
molecules,
such
as
purine
nucleoside
derivatives,
were
well-suited
for
this
transformation,
affording
corresponding
products
in
moderate-to-good
yields.
method
provides
an
strategy
synthesizing
trifluoroisopropyl
molecules
drug
discovery.
Язык: Английский
Transition-Metal-Free Hydrodefluoroamination of Trifluoromethyl Enones for the Synthesis of α-Fluoroenamides
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(14), С. 10299 - 10310
Опубликована: Июль 2, 2024
A
three-component
strategy
was
developed
to
enable
hydrodefluoroamination
of
β-trifluoromethyl
enones
by
selectively
activating
two
C(sp3)-F
bonds
in
the
trifluoromethyl
group.
The
method
involved
a
sequence
carbonyl
reduction,
hydrodefluorination,
and
defluoroamination
under
transition-metal-free
conditions.
Synthetically
useful
(E)-stereospecific
α-fluoroenamides
were
obtained
good
yields
with
diverse
functional
group
tolerance,
which
could
be
easily
transformed
into
valuable
organofluorides
heterocycles.
auxiliary
exerts
both
electronic
steric
impacts
on
CF3-alkenes,
allowing
for
controllable
selective
defluorination.
Язык: Английский
Rhodium-Catalyzed Enantioselective Hydrosilylation of 1,1-Disubstituted Enamides
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 8, 2024
Catalytic
hydrosilylation
of
1,1-disubstituted
enamides
is
one
the
most
challenging
and
synthetically
useful
processes
in
organosilicon
chemistry
asymmetric
catalysis.
Herein,
we
report
a
rhodium-catalyzed
enantioselective
α-arylenamides
with
substituted
hydrosilanes
aid
chiral
P-ligand,
including
newly
developed
spirophosphite
ligands,
giving
various
β-silylated
amides
excellent
yields
good
to
enantioselectivities
(98:2
er
after
recrystallization).
In
addition,
amines
can
be
obtained
by
further
functionalization
product.
Язык: Английский