The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12725 - 12738
Опубликована: Авг. 9, 2024
The
enantioenriched
lactams
disclosed
in
this
work
are
synthesized
concisely
four
steps.
In
the
penultimate
reaction,
a
benzylamine
species
complexes
with
chiral
phosphoric
acid
to
produce
benzo-fused
δ-lactams
equipped
an
all-carbon
quaternary
stereocenter.
Partial
and
full
reductions
were
carried
out
on
ester
amide
moieties,
Suzuki–Miyaura
cross-coupling
expanded
molecule
from
aromatic
ring.
Finally,
our
method
was
successful
at
>1
g
scale,
indicating
that
has
important
practical
use.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
study
investigates
the
potential
of
boron
trifluoride
etherate
(BF3·OEt2)
to
trigger
unprecedented
reactions
2-oxoaldehydes
with
nitriles
and
amides/sulphonamides.
In
contrast
mechanism
in
conventional
reactions,
α-carbonyl
group
induces
a
cyclization
pathway
be
followed
when
reacting
nitriles,
yielding
4-amidooxazoles.
Additionally,
weak
nucleophiles
produce
β-keto
BF3·OEt2
catalysis
offers
novel,
efficient,
operationally
simple
synthetic
route
these
valuable
compounds,
showcasing
versatility
Lewis
acids
organic
transformations.
Alkyne-
and
alkene-tethered
acyl
fluorides
undergo
intramolecular
carbofluorination
via
fluoride
recycling
using
catalytic
TrBF4.
Excellent
stereoselectivity
is
observed
for
the
alkyne
addition,
enabling
access
to
novel
fluorinated
indan-2-ones
(all
≥95:5
E/Z)
cyclopentan-2-ones
(85:15
E/Z).
Fluorinated
chroman-2-ones
tertiary
alkyl
can
also
be
synthesized
this
method,
comparing
favorably
previously
reported
protocols
that
employ
expensive
metal
catalysts
under
harsher
conditions.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 11, 2025
Guanidines
make
up
a
class
of
compounds
with
important
applications
in
catalysis
and
medicinal
chemistry.
In
this
systematic
study,
we
report
on
the
guanylation
aliphatic
amines,
anilines,
(sulfon)amides,
ureas,
carbamates
by
repurposing
HATU,
common
amide
coupling
reagent.
The
products
are
2-substituted
1,1,3,3-tetramethylguanidines
(TMGs),
group
sterically
hindered
superbases.
reaction
guanidinium
salt
amines
has
been
regarded
as
an
unwanted
side-reaction
coupling,
yet
exact
mechanistic
details
have
unclear.
Our
investigation
shows
that
is
highly
dependent
nature
nitrogen
nucleophile.
findings
were
applied
two
fronts:
minimizing
competing
reactions
well
maximizing
simple
one-step
synthesis
broad
variety
TMGs,
including
late-stage
functionalization
pharmaceuticals.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(22), С. 2981 - 2987
Опубликована: Июнь 30, 2023
Comprehensive
Summary
A
practical
one‐pot
preparation
of
carbamoyl
fluorides
from
easily
obtained
pyridine
N
‐oxide,
commercially
available
secondary
amines
and
synthetically
versatile
difluorocarbene
precursors
(Ruppert‐Prakash
reagent
or
Chen's
reagent)
was
developed
herein,
which
dexterously
resorted
to
the
oxidation
by
external
‐oxide
produce
toxic
gaseous
fluorophosgene
in
situ
.
Notable
features
this
method
include
nice
functionality
tolerance,
late‐stage
modification
drug
molecules
recovery
recycle
quinoline.
Bulletin of the Chemical Society of Japan,
Год журнала:
2023,
Номер
96(9), С. 872 - 886
Опубликована: Июль 27, 2023
Abstract
This
Award
Account
reports
our
recent
studies
concerning
the
catalytic
transformations
that
involve
a
non-classical
mode
of
molecular
activation
by
tertiary
phosphines
and
N-heterocyclic
carbenes
(NHCs).
Regarding
organophosphine
catalysis,
we
successfully
designed
reactions
based
on
P(III)/P(V)
redox
couple.
A
protocol
for
generating
pentacoordinate
P(V)
species
was
devised
reaction
phosphines,
acyl
fluorides
alkynoates.
The
ability
thus
generated
fluorophosphoranes
to
participate
in
ligand
coupling
metathesis
with
organosilicon
nucleophiles
enables
synthetic
are
otherwise
unattainable,
including
intermolecular
carbofluorination
alkynes
hydroalkenylation
enol
ethers.
nucleophilic
NHC
use
imidazolium-based
NHCs
can
generate
deoxy-Breslow
intermediates
sufficiently
promote
aromatic
substitution
aryl
halides,
ethers
anilides.
also
be
used
styrene
derivatives,
allowing
generation
series
ylide
serve
as
non-stabilized
vinyl
anion
equivalents.
These
results
demonstrate
involving
carbanions
conducted
under
conditions
without
strong
organometallic
nucleophiles.
Organic Letters,
Год журнала:
2023,
Номер
25(48), С. 8558 - 8563
Опубликована: Ноя. 21, 2023
The
synthesis
of
carbamoyl
fluorides
via
visible-light
induced
DDQ
catalysis
secondary
amines
is
described.
This
protocol
employs
sodium
trifluorosulfinate
and
molecular
oxygen
for
the
in
situ
generation
carbonyl
difluoride,
which
reacted
with
to
afford
corresponding
efficiently.
Moreover,
are
easily
transformed
synthetically
useful
compounds
under
mild
reaction
conditions.
Chemical Communications,
Год журнала:
2024,
Номер
60(66), С. 8700 - 8703
Опубликована: Янв. 1, 2024
We
describe
a
palladium-catalyzed
Suzuki-type
cross-coupling
reaction
of
2-pyridyl
carbamoyl
fluorides
with
boronic
acids,
which
provides
entry
to
medicinally
relevant
pyridyl
amides.
Mechanistic
studies,
including
the
synthesis
and
reactivity
Pd-F
complexes,
reveal
importance
both
fluoride
electrophile
nitrogen
directing
group
for
aiding
reactivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(5)
Опубликована: Дек. 9, 2023
Abstract
In
this
paper,
we
report
BF
3
⋅
OEt
2
as
a
catalyst
to
shuttle
equivalents
of
HF
from
fluoroalkane
an
alkyne.
Reactions
terminal
and
internal
aliphatic
alkynes
led
formation
difluoroalkane
products,
while
diarylalkynes
can
be
selectively
converted
into
fluoroalkenes.
The
method
tolerates
numerous
sensitive
functional
groups
including
halogen,
protected
amine,
ester
thiophene
substituents.
Mechanistic
studies
(DFT,
probe
experiments)
suggest
the
is
involved
in
both
defluorination
fluorination
steps,
with
acting
Lewis
acid
weak
base
that
mediates
proton
transfer.
certain
cases,
interconversion
fluoroalkene
products
was
found
reversible.
new
catalytic
system
applied
demonstrate
proof‐of‐concept
recycling
poly(vinylidene
difluoride).
