Angewandte Chemie,
Год журнала:
2023,
Номер
135(42)
Опубликована: Авг. 12, 2023
Abstract
An
unprecedented
Pd‐catalyzed
fluorinative
bifunctionalization
of
aziridines
and
azetidines
was
successfully
developed
via
regioselective
C−C
C−F
bond
cleavage
gem‐difluorocyclopropanes,
leading
to
various
β,β′‐bisfluorinated
amines
β,γ‐bisfluorinated
amines.
This
reaction
achieved
by
incorporating
a
2‐fluorinated
allyl
group
fluorine
atom
scissored
from
gem‐difluorocyclopropane
in
100
%
economy
for
the
first
time.
The
mechanistic
investigations
indicated
that
underwent
amine
attacking
palladium
complex
generate
η
2
‐coordinated
N‐allyl
aziridine
followed
fluoride
ligand
transfer
affording
final
β‐
γ‐fluorinated
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(42)
Опубликована: Авг. 12, 2023
Abstract
An
unprecedented
Pd‐catalyzed
fluorinative
bifunctionalization
of
aziridines
and
azetidines
was
successfully
developed
via
regioselective
C−C
C−F
bond
cleavage
gem‐difluorocyclopropanes,
leading
to
various
β,β′‐bisfluorinated
amines
β,γ‐bisfluorinated
amines.
This
reaction
achieved
by
incorporating
a
2‐fluorinated
allyl
group
fluorine
atom
scissored
from
gem‐difluorocyclopropane
in
100
%
economy
for
the
first
time.
The
mechanistic
investigations
indicated
that
underwent
amine
attacking
palladium
complex
generate
η
2
‐coordinated
N‐allyl
aziridine
followed
fluoride
ligand
transfer
affording
final
β‐
γ‐fluorinated
ACS Catalysis,
Год журнала:
2023,
Номер
13(11), С. 7310 - 7321
Опубликована: Май 15, 2023
Anilines
are
important
moieties
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Although
para-selective
functionalization
of
anilides
tertiary
anilines
is
well
established,
unprotected
have
posed
a
challenge.
Herein,
we
report
visible-light-mediated
Ru(II)-catalyzed
para-alkylation
anilines.
The
distinct
Ru(II)–aniline
complex
enabled
the
reaction
to
proceed
with
extremely
high
efficiency
(2
h)
under
mild
conditions.
good
functional
group
tolerance
allowed
late-stage
even
aggregation-induced
emission
luminogen
labeling
natural
products
drugs.
A
mechanistic
investigation
suggests
that
crucial
for
both
triggering
controlling
para-selectivity.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(3)
Опубликована: Окт. 14, 2022
A
three-component
reaction
of
N,
N-disubstituted
aniline,
α-diazo
ester,
and
an
allylic
electrophile
has
been
realized
by
[Rh(II)]2
/Xantphos
catalysis,
providing
a
direct
access
to
various
aniline
derivatives
bearing
diaryl
quaternary
centers
in
good
yields.
The
synthetic
utility
this
protocol
was
demonstrated
facile
derivatization
the
products
for
preparation
biologically
relevant
molecules
structural
scaffolds,
which
offers
high
potential
increasing
molecular
diversity.
Mechanistic
studies
identified
α,
α-diarylacetate
species
as
active
intermediate,
thereby
revealing
presence
C(sp2
)-H
functionalization
derivatives/allylic
alkylation
cascade
attractive
catalytic
transformation.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(36), С. 20031 - 20040
Опубликована: Авг. 29, 2023
Albeit
notable
endeavors
in
enantioselective
carbene
insertion
into
X–H
bonds
(X
=
C,
O,
N,
S,
Si,
B),
the
catalytic
asymmetric
P–H
reactions
still
stand
for
a
long-lasting
challenge.
By
merging
transition-metal
catalysis
with
organocatalysis,
we
achieve
scalable
transformation
between
diazo
pyrazoleamides
and
H-phosphine
oxides
that
upon
subsequent
reduction
delivers
wide
variety
of
optically
active
β-hydroxyl
phosphine
good
yields
high
enantioselectivity.
The
achiral
copper
catalyst
fosters
carbenoid
bond,
while
chiral
cinchona
alkaloid-derived
organocatalyst
controls
outcome.
Density
functional
theory
(DFT)
calculations
further
reveal
chelates
to
organocatalyst,
enhances
its
acidity,
accordingly
promotes
proton
transfer.
Our
work
showcases
potential
combining
organocatalysis
realize
elusive
reactions.
Chemical Science,
Год журнала:
2024,
Номер
15(33), С. 13240 - 13249
Опубликована: Янв. 1, 2024
The
enantioselective
and
diastereoselective
synthesis
of
atropisomeric
hydrazides
with
defined
vicinal
central
axial
chirality
via
ternary
catalysis
in
a
one-pot
process
is
reported.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 28, 2025
The
attractive
force
between
two
oppositely
charged
ions
can
constitute
a
powerful
design
tool
in
selective
catalysis.
Enzymes
make
extensive
use
of
ionic
interactions
alongside
variety
other
noncovalent
interactions;
recent
years
have
seen
synthetic
chemists
begin
to
seriously
explore
these
catalyst
designs
that
also
incorporate
reactive
transition
metal.
In
isolation,
single
interaction
exhibits
low
directionality,
but
many
successful
systems
they
exist
additional
which
provide
high
degree
organization
at
the
selectivity-determining
state.
Even
situations
with
key
interaction,
directionality
is
not
always
detrimental,
and
even
be
advantageous,
conferring
generality
catalyst.
This
Review
explores
approaches
utilize
control
selectivity
metal
It
divided
into
halves:
first,
occurs
outer
sphere
complex,
using
ligand
or
bound
an
anion;
second,
bears
formal
charge,
associated
counterion.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(7), С. 1378 - 1385
Опубликована: Янв. 1, 2024
An
efficient
transition-metal/photocatalyst-free
visible-light-driven
one-pot
three-component
reaction
between
thianthrenium
salts,
carbon
disulfide
and
amines
under
air
atmosphere
for
the
preparation
of
S
-aryl
dithiocarbamates
is
developed.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(20)
Опубликована: Март 19, 2024
Abstract
Herein,
multiple
types
of
chiral
Os(II)
complexes
have
been
designed
to
address
the
appealing
yet
challenging
asymmetric
C(sp
3
)−H
functionalization,
among
which
Os(II)/Salox
species
is
found
be
most
efficient
for
precise
stereocontrol
in
realizing
amidation.
As
exemplified
by
enantioenriched
pyrrolidinone
synthesis,
such
tailored
catalyst
efficiently
enables
an
intramolecular
site‐/enantioselective
amidation
γ‐position
dioxazolone
substrates,
benzyl,
propargyl
and
allyl
groups
bearing
various
substituted
forms
are
well
compatible,
affording
corresponding
γ‐lactam
products
with
good
er
values
(up
99
:
1)
diverse
functionality
(>35
examples).
The
unique
performance
advantage
developed
system
terms
catalytic
energy
profile
induction
has
further
clarified
integrated
experimental
computational
studies.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(10), С. 1623 - 1628
Опубликована: Май 5, 2023
Abstract
A
rhodium‐catalyzed
cascade
1,3‐sulfinate
migration,
intermolecular
[3+2]
annulation
of
1‐sulfonyl‐1,2,3‐triazoles
and
indoles
was
achieved.
The
one‐pot
protocol
provided
a
method
to
construct
cyclopenta[
b
]indoles
bearing
four
stereocenters
in
45%
99%
yields
with
1.6:1
>20:1
diastereoselectivities.
In
addition,
could
be
transformed
into
variety
functionalized
compounds,
demonstrating
the
synthetic
value
this
migration‐annulation
strategy
ring
system
synthesis.
magnified
image
