A
metal-free
intramolecular
cyclopropanation
of
CF3-imidoyl
sulfoxonium
ylides
with
styrenes
was
developed,
affording
cyclopropane-fused
quinolines.
This
strategy
provides
efficient
access
to
diverse
trifluoromethyl-substituted
dihydro-1H-cyclopropa[c]quinolines
under
mild,
transition-metal-free
conditions.
Notably,
the
ylide
generation
and
subsequent
could
proceed
in
a
one-pot
fashion,
products
good
yields.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(15), С. 8417 - 8429
Опубликована: Март 23, 2023
Mechanistic
understanding
of
asymmetric
induction
plays
a
crucial
role
in
designing
new
catalytic
reactions.
Reported
herein
is
atroposelective
access
to
C-N
axially
chiral
isoquinolones
via
rhodium-catalyzed
C-H
activation
N-alkoxy
benzamides
and
annulation
with
imidoyl
sulfoxonium
ylides.
The
coupling
system
proceeded
excellent
functional
group
tolerance,
different
conditions
were
identified
afford
one
or
the
other
enantiomeric
product
each
enantioselectivity
for
representative
class
ylide
reagent,
thus
making
both
enantiomers
readily
available
using
same
catalyst.
Experimental
computational
studies
revealed
pathway
alkylation
enantio-determining
formal
nucleophilic
substitution-C-N
cyclization
that
mediated
by
rhodium
catalyst
σ-bond
metathesis
as
mechanism.
Computational
indicated
solvent-dependent
enatiodivergence
originated
from
levels
neutral
versus
cationic
species.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(31), С. 6246 - 6276
Опубликована: Янв. 1, 2024
Recent
advances
in
the
preparation
of
trifluoromethyl-containing
heterocyclics
via
trifluoromethyl
building
block
strategies
over
period
from
2019
to
present
are
systematically
summarized
and
discussed.
Organic Letters,
Год журнала:
2022,
Номер
24(48), С. 8864 - 8869
Опубликована: Дек. 1, 2022
An
efficient
and
straightforward
approach
for
the
synthesis
of
trifluoromethyl-decorated
benzo[de][1,8]naphthyridines
has
been
achieved
via
Rh(III)-catalyzed
dual
C-H
activation
cascade
annulation
benzimidates
CF3-imidoyl
sulfoxonium
ylides.
The
novel
transformation
involves
formation
four
new
chemical
bonds
along
with
release
two
molecules
dimethyl
sulfoxide
(DMSO)
one
molecule
each
ethanol
amine.
optoelectronic
properties
obtained
fused
aromatic
products
have
investigated
by
recording
UV-vis
absorption
emission
spectra.
Chemical Communications,
Год журнала:
2023,
Номер
59(33), С. 4872 - 4890
Опубликована: Янв. 1, 2023
Recent
advances
in
the
direct
synthesis
of
trifluoromethyl-containing
heterocycles
from
trifluoroacetimidoyl
chlorides
(TFAICs)
and
derivatives,
including
trifluoroacetimidohydrazides
(TFAIHs)
CF3-imidoyl
sulfoxonium
ylides
(TFISYs),
are
systematically
summarized
discussed.
The
cascade
annulation
reactions
synthons
with
suitable
coupling
partners
have
emerged
as
a
powerful
promising
tool
for
construction
variety
trifluoromethyl-substituted
heterocycles.
Compared
other
building
blocks,
TFAICs
derivatives
notable
merits
easy
availability
handling,
relative
stability
safety,
high
reactivity.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(15), С. 3843 - 3848
Опубликована: Янв. 1, 2023
We
have
developed
a
Rh(
iii
)-catalyzed
C–H
activation/chemodivergent
annulation
of
N
-carbamoylindoles
with
TFISYs,
allowing
facile
access
to
variety
trifluoromethyl-substituted
(dihydro)pyrimidoindolones
high
efficiency.
Solvents
play
critical
role
in
the
selectivity
reaction.
Organic Letters,
Год журнала:
2024,
Номер
26(1), С. 62 - 67
Опубликована: Янв. 3, 2024
We
have
found
a
chameleonic
reactivity
of
imidoyl
sulfoxonium
ylides.
On
the
one
hand,
ylides
react
with
electron-deficient
reagents,
such
as
alkynyl
esters,
to
lead
formation
1,2-dihydro-pyridines.
The
methyl
group
attached
sulfur
atom
acts
methylene
donor.
other
pyridinium
1,4-zwitterionic
thiolates,
which
leads
functionalized
pyrroles.
Both
transformations
feature
mild
reaction
conditions
and
good
functional
tolerance.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(11), С. 1770 - 1776
Опубликована: Март 21, 2023
Abstract
Rh‐catalyzed
C−H
activation
of
arenes
for
oxidative
annulations
with
alkynes
stands
out
as
a
protocol
polycyclic
scaffolds.
This
perspective
drives
us
to
disclose
herein
rhodium
catalyzed
regioselective
triple
annulation
enaminones
hydroxyl‐alkynoates
via
double
functionalization
naphtho‐pyran
Secondary
coordination
OH
in
alkynoate
dictated
the
regioselectivity.
Initial
lactonization
occurred
chemoselectively
on
enamine
part
carbo
rhodation
followed
by
reductive
elimination.
was
scalable
and
has
shown
high
functionality
tolerance.
KIE
studies
were
done
get
insight
mechanism,
some
downstream
transformations
achieved
show
synthetic
potential
method.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(9), С. 1521 - 1525
Опубликована: Март 31, 2023
Abstract
An
approach
for
the
construction
of
5‐trifluoromethyl‐1,4‐dihydro‐1,2,4‐triazines
has
been
developed
via
base‐mediated
[3+3]
cycloaddition
in‐situ
generated
nitrile
imines
and
CF
3
‐substituted
imidoyl
sulfoxonium
ylides.
The
metal‐free
protocol
is
characterized
by
readily
available
starting
materials,
mild
conditions,
a
broad
substrate
scope,
high
efficiency,
good
synthetic
prospect,
scalability.
magnified
image
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(19), С. 3382 - 3386
Опубликована: Авг. 16, 2023
Abstract
A
heating‐induced
desulfuration
annulation
of
pyridinium
1,4‐zwitterionic
thiolates
and
CF
3
‐substituted
imidoyl
sulfoxonium
ylides
has
been
achieved,
allowing
a
route
to
biologically
important
5‐trifluoromethylpyrroles.
The
transformation
proceeds
through
an
unusual
((3+3)‐1)
pathway
under
metal‐free
conditions
with
the
extrusion
4‐methoxypyridine,
sulfur
DMSO.
scale‐up
reaction
further
obtained
pyrrole
products
have
performed
demonstrate
synthetic
utility
developed
method.
