Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 30, 2024
Abstract
Selective
C−F
bond
activation
through
a
radical
pathway
in
the
presence
of
multiple
C−H
bonds
remains
formidable
challenge,
owing
to
extraordinarily
strong
strength
bond.
By
aid
density
functional
theory
calculations,
we
disclose
an
innovative
concerted
electron‐fluoride
transfer
mechanism,
harnessing
unique
reactivity
Lewis
base‐boryl
radicals
selectively
activate
resilient
fluoroalkanes.
This
enables
direct
abstraction
fluorine
atom
and
subsequent
generation
alkyl
radical,
thus
expanding
boundaries
halogen
reactions.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 1294 - 1304
Published: Jan. 7, 2025
Given
the
widespread
presence
of
spirocyclic
scaffolds
in
natural
products
and
pharmacologically
relevant
synthetic
compounds,
development
efficient
methodologies
for
their
construction
holds
great
importance
medicinal
chemistry
pharmaceutical
research.
In
this
study,
a
general
photochemical
dearomative
spirocyclization
nonactivated
arenes
has
been
established.
The
key
to
method
lies
ability
amine-borane
radicals
activate
aryl
bromides
iodides
via
halogen-atom
transfer,
thereby
allowing
conversion
halides
into
corresponding
subsequent
chemodivergent
transformations.
remarkable
compatibility
versatility
1,4-difunctionalization
is
showed
by
rapid
assembly
structurally
diverse
1,4-cyclohexadiene-based
spirocycles
incorporating
oxindole,
indoline,
or
dihydrobenzofuran
subunits.
Moreover,
potential
utility
protocol
exemplified
formal
total
synthesis
vasopressin
V2
receptor
antagonist
Satavaptan.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(48), P. 8722 - 8726
Published: Nov. 29, 2023
A
photochemical
halogen-atom
transfer
(XAT)
method
for
generating
sulfonyl
radicals
from
aryl
fluorides
has
been
developed.
It
allows
the
hydrosulfonylation
of
unactivated
alkenes,
which
was
challenging
to
achieve
through
our
previous
single-electron
route.
This
reaction
excellent
functional
group
tolerance
and
substrate
scope
under
mild
conditions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
The
ligated
boryl
radical
(LBR)
has
emerged
as
a
potent
tool
for
activating
alkyl
halides
in
transformations
through
halogen-atom
transfer
(XAT).
However,
unactivated
chlorides
still
present
an
open
challenge
this
strategy.
We
herein
describe
new
activation
mode
of
the
LBR
to
construct
C(sp
Synthesis,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Abstract
Compounds
bearing
mono-
and
dibromomethyl
groups
are
extensively
utilized
in
synthetic
medicinal
chemistry.
In
this
regard,
selective
debromination
of
readily
or
easily
accessible
tribromomethyl
compounds
offers
a
direct
efficient
method
to
access
those
two
moieties.
work,
we
introduced
Lewis
base–borane-mediated
hydrodebromination
via
ionic
radical
pathway.
Using
4-(dimethylamino)pyridine–borane
(DMAP-BH3)
as
hydride
donor,
monohydrodebromination
was
achieved
nucleophilic
substitution
by
hydride,
delivering
groups.
On
the
other
hand,
treatment
with
an
N-heterocyclic
carbene–borane
(NHC-BH2CN)
boryl
precursor
presence
dilauroyl
peroxide
(DLP)
initiator
afforded
monobromomethyl
through
consecutive
bromine
atom
abstractions
cleave
C–Br
bonds.
Various
group
acetamides
acetates
were
applied
developed
protocol,
showcasing
good
functional
tolerance
broad
substrate
scope.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
new
photocatalytic
approach
by
using
the
assembly
of
DABCO
A1
and
B
2
Nep
B1
has
been
established
to
enable
cross-coupling
organohalides
alkenes
for
C(sp
3
)–C(sp
)
bond
formation.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 12, 2024
β-Amino
acids
serve
as
crucial
building
blocks
for
a
broad
range
of
biologically
active
molecules
and
peptides
with
potential
peptidomimetics.
While
numerous
methods
have
been
developed
the
synthesis
β-amino
acids,
most
them
require
multistep
preparation
specific
reagents
substrates,
which
limits
their
synthetic
practicality.
In
this
regard,
homologative
transformation
abundant
readily
available
α-amino
would
be
an
attractive
approach
acid
synthesis.
Herein,
we
disclose
development
sequential
process
to
provide
diverse
from
derivatives
commercially
phosphonium
ylides
via
visible
light
photoredox
catalysis.
two-step
protocol,
function
bifunctional
linchpin:
they
act
carbon
nucleophile
forge
C-C
bond
in
first
step
carbon-centered
radical
source
modifications
scaffold
second
step.
The
orthogonal
activation
these
reactivities
under
mild
photocatalytic
conditions
enables
modular
three-component
assembly
access
dipeptides
high
structural
diversity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 18, 2024
A
new
iron-catalyzed
three-component
perfluoroalkylarylation
of
styrenes
with
alkyl
halides
and
arenes
has
been
established.
Alkyl
undergo
halogen
atom
transfer
methyl
radicals
to
form
in
reactions
initiated
by
a
combination
