European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(36)
Опубликована: Авг. 23, 2022
Abstract
Unsaturated
triflimides,
especially
homoallylic
triflimide
species,
are
rarely
assessable.
Herein,
we
disclose
a
Ca(NTf
2
)
/HFIP‐mediated
direct
chemo‐,
regio‐,
and
stereoselective
rearrangement
of
diverse
cyclopropyl
carbinols
to
exclusive
E
‐homoallylic
triflimides
in
moderate
excellent
yields
at
room
temperature,
which
was
used
as
both
the
OH
activator
anion
source.
This
protocol
shows
substrate/functional
group
tolerance
with
an
emphasis
on
those
substrates
bearing
strong
electron‐withdrawing
functional
groups.
ACS Organic & Inorganic Au,
Год журнала:
2024,
Номер
4(3), С. 287 - 300
Опубликована: Март 4, 2024
In
the
past
5
years,
hexafluoroisopropanol
(HFIP)
has
been
used
as
a
unique
solvent
or
additive
to
enable
challenging
transformations
through
substrate
activation
and
stabilization
of
reactive
intermediates.
this
Review,
we
aim
at
describing
difunctionalization
processes
which
were
unlocked
when
HFIP
was
involved.
Specifically,
focus
on
cyclizations
additions
alkenes,
alkynes,
epoxides,
carbonyls
that
introduce
wide
range
functional
groups
interest.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 20, 2025
The
development
of
practical
and
selective
strategies
for
deuterium
incorporation
to
construct
deuterated
molecules,
particularly
deuterium-labeled
amino
acids,
has
become
as
a
growing
focus
basic
research,
yet
it
remains
formidable
challenge.
Herein,
we
present
bioinspired
calcium-HFIP-mediated
site-selective
reductive
deutero-amination
α-oxo-carbonyl
compounds
with
amines.
Utilizing
d2-Hantzsch
ester
the
source,
this
reaction
attains
remarkable
deuteration
efficiency
(>
99%
deuteration).
It
enables
synthesis
N-α-deuterated
acid
motifs
wide
range
functionality,
evidenced
by
over
130
examples.
method
exhibits
compatibility
diverse
substrates,
such
peptides,
drug
natural
products
bearing
different
substituents.
Moreover,
application
strategy
in
DNA-tagged
acids/peptides
been
demonstrated.
This
work
offers
an
efficient
innovative
solution
chemistry
holds
substantial
potential
organic
synthesis,
medicinal
chemistry,
chemical
biology.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(12)
Опубликована: Фев. 14, 2024
Abstract
Hexafluoroisopropanol
(HFIP)
stands
out
as
a
versatile
solvent
in
synthetic
chemists’
repertoire,
facilitating
diverse
array
of
intricate
chemical
reactions.
It
demonstrates
multifaceted
role
that
extends
beyond
conventional
uses
and,
many
cases,
the
mechanism
appears
to
be
complicated.
This
feature
article
elucidates
significance
HFIP
context
Lewis
and
Brønsted
acid‐catalyzed
reactions
with
specific
emphasis
on
regio‐
stereoselective
functionalization
unsaturated
carbon‐carbon
bonds.
Organic Letters,
Год журнала:
2022,
Номер
24(41), С. 7502 - 7506
Опубликована: Окт. 11, 2022
A
highly
regioselective
synthesis
of
spiro[benzofuran-2,2'-furan]-3-ones
has
been
explored
via
Lewis
acid-catalyzed
[3
+
2]
cyclization
iodonium
ylides
with
azadienes.
The
acidity
the
acid
was
significantly
strengthened
strong
hydrogen
bond
donors,
thereby
promoting
enolization
isomerization
for
subsequent
cycloaddition.
This
reaction
compatible
a
broad
range
substrates
under
mild
conditions,
and
efficiently
delivered
spiro-heterocycles
excellent
stereoselectivity.
Organic Letters,
Год журнала:
2023,
Номер
25(14), С. 2504 - 2508
Опубликована: Март 31, 2023
Direct
access
to
the
polyfluorinated
lactams
through
Ca(NTf2)2
catalyzed
by
either
reductive
amination
of
biomass-derived
keto
acids
with
amines
or
amino
carbonyl
derivatives
under
solvent-free
conditions
is
realized.
The
two
versatile
protocols
display
chemospecificity
and
good
substrate
tolerance
deliver
five-
eight-membered
diverse
functionality
substitution
patterns.
robustness
methodology
further
demonstrated
subsequent
application
in
late-stage
functionalization
drug
molecules.
Organic Letters,
Год журнала:
2023,
Номер
25(45), С. 8095 - 8099
Опубликована: Ноя. 8, 2023
A
mild
and
general
protocol
involving
amnio-
oxyselenation
of
diverse
alkenes
for
the
efficient
synthesis
organo-Se
compounds
is
achieved
via
an
environmentally
benign
calcium-catalyzed
three-component
reaction.
This
selenofunctionalization
reaction
exhibits
excellent
substrate/functional
group
tolerance
high
levels
chemo-
regioselectivity.
Its
utility
was
exemplified
in
late-stage
functionalization
even
aggregation-induced
emission
luminogen
labeling
compounds.
Organic Letters,
Год журнала:
2024,
Номер
26(29), С. 6274 - 6278
Опубликована: Июль 15, 2024
A
calcium-mediated
three-component
selenylation
of
gem-difluoroalkenes
using
alcohols
as
nucleophiles
and
N-(phenylseleno)phthalimide
the
agent
has
been
developed
for
efficient
synthesis
various
α,α-difluoroalkyl-β-selenides.
This
reaction
exhibits
broad
substrate
functional
group
tolerance,
along
with
high
levels
chemo-
regioselectivity.
Additionally,
synthetic
utility
transformation
in
late-stage
functionalization
drug
molecules
was
demonstrated.
Abstract
Selective
and
concise
construction
of
ring
systems
that
are
ubiquitous
skeletons
across
chemistry,
drugs
materials,
is
indispensable
for
human
life.
Of
note,
directed
C−H
annulation
with
alkynes
the
expedient
delivery
holds
great
importance,
featuring
step‐
atom‐economy,
mild
conditions,
broad
substrate
scope.
However,
regioselectivity
issues
remained
when
using
unsymmetrical
annulation.
Herein,
we
summarized
recent
achievements
towards
solving
this
problem
by
developing
directing
groups,
metal
catalysts,
versatile
traceless
functionality
ensure
overall
regioselectivity,
enantioselectivity,
efficiency,
synthetic
application.
We
hope
concept
will
promote
further
development
precise
functional
molecules
alkynes.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(17)
Опубликована: Дек. 28, 2022
The
solvent
effects
in
Friedel-Crafts
cycloalkylation
of
epoxides
and
Cope
rearrangement
aldimines
were
investigated
by
using
ab
initio
molecular
dynamics
simulations.
Explicit
treatments
applied
for
both
reactants
solvents.
reaction
mechanisms
elucidated
via
free
energy
calculations
based
on
metadynamics
results
reveal
that
reactions
proceed
a
concerted
fashion.
Key
solvent-substrate
interactions
are
identified
from
the
structures
transition
states
with
explicit
molecules.
remarkable
promotion
effect
hexafluoroisopropanol
is
ascribed
to
synergistic
H-bonding
networks
C-H/π
substrates.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(26)
Опубликована: Апрель 8, 2024
Abstract
A
new
strategy
for
the
synthesis
of
3‐substituted
phthalides
has
been
developed
via
a
Lewis
acid‐catalyzed
intramolecular
ring
opening
aziridines
with
esters.
Broad
substrate
scope,
good
yields
and
mild
conditions
made
cyclization
reaction
very
suitable
rapid
construction
libraries
phthalide
compounds.
