Abstract
p
K
a
values
of
C−H
bonds
remain
unreported
and
challenging
in
fluorous
solvents
because
these
solvents’
unique
physicochemical
properties,
although
they
have
been
measured,
theorized
predicted
successfully
water
common
organic
solvents.
Herein,
new
CF
3
SO
2
‐substituted
anchor
compound
designed
for
matching
the
properties
polar
fluorinated
arenes
is
synthesized.
Its
self‐dissociation
constants
are
used
as
bases
experimentally
determining
36
compounds
them.
These
determined
exhibit
excellent
linear
free‐energy
relationships
correlate
well
with
their
corresponding
DFT‐calculated
values.
data
indicate
that
thermodynamically
more
favorable
deprotonation
ketone
derivatives
than
acetonitrile
reaction
media,
resulting
enhanced
deprotonation‐promoted
CO
fixation.
The
this
work
can
be
an
important
guidance
tool
reactions
involving
formation
cleavage
arenes.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
The
direct
synthesis
of
C(sp3)-rich
architectures
is
a
driving
force
for
innovation
in
synthetic
organic
chemistry.
Such
scaffolds
impart
beneficial
properties
onto
drug
molecules
that
correlate
with
greater
clinical
success.
Consequently,
there
strong
impetus
to
develop
new
methods
by
which
access
sp3-rich
from
commercial
feedstocks,
such
as
alkenes.
Herein,
we
report
three-component
aminoalkylation
reaction
utilizes
the
principles
triple
radical
sorting
regioselectively
add
N-centered
and
C-centered
radicals
across
This
process
relies
upon
photoredox
catalysis
transform
alkyl
bromides
reductively
activated
precursors
into
high-energy
species
redox-neutral
fashion.
A
broad
scope
coupling
partners
demonstrated,
multiple
applications,
including
facile
syntheses
pharmacophoric
substituted
N-heterocycles.
Singly
occupied
molecular
orbital
(SOMO)
activation
of
in
situ
generated
enamines
has
achieved
great
success
(asymmetric)
α-functionalization
carbonyl
compounds.
However,
examples
on
the
use
this
mode
transformations
other
functional
groups
are
rare,
and
combination
SOMO
with
transition
metal
catalysis
is
still
less
explored.
In
area
deoxygenative
functionalization
amides,
intermediates
such
as
iminium
ions
were
often
to
result
formation
α-functionalized
amines.
contrast,
direct
deoxygenation
amides
β-functionalized
amines
highly
appealing
yet
remains
scarcely
investigated.
Here,
a
arylation
aryl
halides
was
developed
via
multicatalysis
iridium/photoredox/nickel/iridium,
affording
β-aryl
high
efficiency.
The
key
reaction
enamine
synergy
Ni-catalyzed
arylation,
which
conjunction
two
compatible
Ir-catalyzed
reduction
processes.
ACS Catalysis,
Год журнала:
2024,
Номер
14(18), С. 13550 - 13556
Опубликована: Авг. 28, 2024
Photoinduced
enantioselective
strategies
provide
an
efficient
way
to
access
chiral
all-carbon
quaternary
stereocenters.
Compared
with
the
well-developed
metal-catalyzed
asymmetric
conjugate
addition
of
organometallic
reagents
enones,
construction
stereocenters
through
a
radical
process
still
remains
challenging,
especially
for
acyclic
enones
due
their
enhanced
conformational
mobility.
Herein,
we
disclose
photoinduced
cobalt-catalyzed
coupling
α,β-unsaturated
2-acyl
imidazoles
and
α-silylamines
give
β,β-disubstituted
γ-amino
acid
derivatives
carbon
The
facile
protocol
shows
good
functional
group
tolerance
broad
substrate
scope.
corresponding
products
were
obtained
in
generally
yields
(up
96%)
high
enantioselectivities
99:1
e.r.).
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 3, 2024
Catalytic
asymmetric
α-alkylation
of
simple
carboxylic
acid
derivatives
is
a
challenging
issue
due
to
the
difficulties
in
achieving
high
catalytic
efficiency
and
controlling
enantioselectivity.
Herein,
by
using
copper(I)-(R)-DTBM-SEGPHOS
complex
as
catalyst
2-acylimidazoles
pronucleophiles,
general
method
for
accomplished.
Various
alkyl
electrophiles,
including
allyl
bromides,
benzyl
propargyl
bromide,
unactivated
sulfonates,
serve
efficient
alkylation
reagents.
The
reaction
enjoys
advantages
an
easy
protocol,
good
functional
group
tolerance,
2,4,6-Trimethylphenol
found
effective
additive
increase
yields.
Preliminary
1H
NMR
experiments
indicate
precoordination
copper(I)
catalyst,
which
might
acidify
α-hydrogens
allow
facile
generation
stabilized
enolates.
Finally,
synthetic
utility
present
demonstrated
formal
synthesis
AZD2716,
potent
secreted
phospholipase
A2
inhibitor.
Asymmetric
decarboxylative
cross-couplings
of
carboxylic
acids
represent
a
powerful
tool
to
synthesize
chiral
building
blocks
for
medicinal
chemistry
and
material
science.
However,
synthesis
versatile
alkylboron
derivatives
via
asymmetric
C(sp3)-C(sp3)
cross-coupling
from
readily
available
primary
aliphatic
mild
organometallic
reagents
is
still
challenging.
In
this
study,
we
report
visible-light-induced,
Ni-catalyzed
enantioconvergent
unactivated
with
gem-borazirconocene
alkanes,
furnishing
diverse
array
valuable
blocks.
The
broad
substrate
scope,
high
functional
group
tolerance,
the
late-stage
modification
complex
drug
molecules
natural
products
enantioselectivity
demonstrate
synthetic
potential
method.
Mechanistic
investigations
suggest
an
radical-radical
pathway,
wherein
radical
generated
through
single-electron
reduction
ZrIII
species,
representing
unprecedented
example
enantioselective
cross
coupling
in
absence
photocatalysts.
Abstract
Transition
metal‐catalyzed
cross‐coupling
reactions
have
become
a
powerful
and
widely
used
synthetic
approach
for
the
construction
of
both
carbon‐carbon
carbon‐heteroatom
bonds.
These
revolutionized
chemistry
by
enabling
efficient
formation
complex
molecular
architectures.
Among
various
methods
available,
bimolecular
homolytic
substitution
(S
H
2)
reaction
has
emerged
as
an
attractive
versatile
method
C(sp
3
)−C(sp
)
)‐heteroatom
In
recent
years,
significant
progress
been
made
in
development
radical
S
2
reactions,
particularly
those
involving
different
transition
metal
complexes
such
cobalt,
nickel,
iron.
advancements
expanded
scope
allowing
greater
diversity
substrate
compatibility
conditions.
this
review,
we
aim
to
highlight
latest
breakthroughs
mechanistic
insights
into
focusing
on
role
catalysts
facilitating
these
transformations.
We
will
discuss
types
that
employed,
pathways
involved,
potential
applications
synthesis
organic
molecules.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 17, 2024
Asymmetric
decarboxylative
cross-couplings
of
carboxylic
acids
are
powerful
methods
for
synthesizing
chiral
building
blocks
essential
in
medicinal
chemistry
and
material
science.
Despite
their
potential,
creating
versatile
alkylboron
derivatives
through
asymmetric
C(sp
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Июль 10, 2024
Quaternary
carbons
are
embedded
in
various
natural
products,
pharmaceuticals,
and
organic
materials.
However,
constructing
this
valuable
motif
is
far
from
trivial.
Conventional
approaches
mainly
rely
on
classical
polar
disconnections
encounter
bottlenecks
concerning
harsh
conditions,
functional
group
tolerance,
regioselectivity,
step
economy.
In
context,
Kawamata,
Baran,
Shenvi,
co-workers
recently
demonstrated
that
two
feedstock
chemicals,
alkyl
carboxylic
acids
olefins,
could
be
utilized
to
construct
tetrasubstituted
the
presence
of
an
inexpensive
iron
porphyrin
catalyst
a
suitable
reductant
combination
through
quaternization
radical
intermediates.
The
method
enables
access
sterically
encumbered
quaternary
under
mild
robust
conditions.
Taking
complete
detour
conventional
approaches,
present
heteroselective
radical-radical
coupling
simplifies
synthesis
carbon-containing
molecules
innovative
distinctive
disconnection
approach.
