Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(15), P. 8417 - 8429
Published: March 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,
Journal Year:
2024,
Volume and Issue:
22(31), P. 6246 - 6276
Published: Jan. 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,
Journal Year:
2022,
Volume and Issue:
24(40), P. 7288 - 7293
Published: Oct. 4, 2022
A
ruthenium-catalyzed
peri-selective
C-H
activation
and
annulation
of
1-naphthols
with
CF3-substituted
imidoyl
sulfoxonium
ylides
that
uses
hydroxyl
as
a
weakly
coordinating
directing
group
is
disclosed.
The
strategy
provides
facile
practical
route
to
diverse
trifluoromethyl-containing
2,3-dihydrobenzo[de]chromen-2-amines
high
efficiency.
Notable
advantages
this
protocol
include
readily
available
materials,
excellent
regioselectivity,
good
functional
compatibility,
scalability.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(48), P. 8864 - 8869
Published: Dec. 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.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(37), P. 6822 - 6827
Published: Sept. 9, 2022
A
straightforward
strategy
for
the
metal-free
construction
of
trifluoromethyl-containing
pyrazole
derivatives
has
been
achieved
from
readily
available
α-halo
hydrazones
and
CF3-imidoyl
sulfoxonium
ylides.
The
cascade
transformation
proceeds
through
formal
[4+1]
cycloaddition
followed
by
an
unexpected
dual
double
bond
isomerization.
protocol
features
mild
conditions,
easy
operation,
excellent
substrate
compatibility,
good
regioselectivity.
synthetic
utility
is
demonstrated
scale-up
reaction
further
elaboration
obtained
products.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(33), P. 4872 - 4890
Published: Jan. 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,
Journal Year:
2023,
Volume and Issue:
10(15), P. 3843 - 3848
Published: Jan. 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,
Journal Year:
2024,
Volume and Issue:
26(1), P. 62 - 67
Published: Jan. 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,
Journal Year:
2023,
Volume and Issue:
365(9), P. 1521 - 1525
Published: March 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.
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