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.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 25, 2025
Herein,
we
introduce
a
Ni-catalyzed
asymmetric
homobenzylic
hydroamidation
reaction
that
efficiently
addresses
the
dual
challenges
of
achieving
regio-
and
enantioselectivity
in
synthesis
β-(hetero)arylethylamides.
By
employing
transposed
NiH
catalysis
approach,
this
method
facilitates
formation
key
chiral
nickel-amido
intermediates,
enabling
insertion
into
alkenes
to
produce
desired
β-arylamide
products
with
excellent
enantioselectivity.
The
exhibits
high
functional
group
tolerance
utilizes
readily
available
starting
materials
vinylarenes
react
dioxazolone
as
robust
amidating
source.
Notably,
approach
was
successfully
applied
pharmaceutical
compounds
natural
products,
such
Clobenzorex,
Direx,
Selegiline,
Sacubitril,
Cipargamin.
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:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
Decyanation
after
α-functionalization
by
exploiting
the
inherent
properties
of
cyano
groups
enables
strategic
assembly
a
carbon
scaffold.
Herein,
we
demonstrate
an
amine-ligated
boryl
radical-mediated
group
transfer
(CGT)
strategy
malononitriles
under
photocatalytic
conditions.
This
allows
for
cleavage
C(sp3)–CN
and
formation
C(sp3)–D
C(sp3)
to
realize
decyanative
deuteration
cyclization
via
radical-polar
crossover.
Computational
studies
successfully
demonstrated
reactivity
CGT
promoters
can
be
accurately
assessed.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
The
Sonogashira-like
alkynylation
of
alkyl
halides
is
achieved
by
a
photocatalytic
approach
exploiting
amine-ligated
boryl
radicals
as
halogen-atom
transfer
mediators
in
combination
with
alkynyl
sulfones
SOMOphilic
reagents.
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
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(43), P. 9282 - 9287
Published: Oct. 23, 2024
In
this
study,
we
investigated
the
photocatalytic
decarboxylation
of
trimethylamine
carboxyborane
under
mild
conditions,
successfully
generating
boryl
radicals
for
subsequent
borylation
reactions
with
imines
and
various
alkenes.
This
method
exhibited
broad
substrate
compatibility,
including
functionalization
biologically
relevant
molecules.
Our
findings
expand
utility
beyond
its
role
as
a
carbon-monoxide-
drug-releasing
agent,
highlighting
potential
in
radical
chemistry
through
decarboxylation.
work
establishes
robust
foundation
further
exploration
synthetic
application
carboxyborane.
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.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 13, 2025
A
class
of
prearomatic
carboxylic
acid
p-quinol
ester
radical
precursors
has
been
developed
successfully,
which
could
undergo
homolytic
cleavage
the
para
C-O
bond
esters
via
pyridine-boryl
radical-induced
aromatization
in
presence
pyridines
and
diboron
reagents,
affording
corresponding
alkyl
decarboxylation
from
carboxyl
situ.
In
addition,
were
further
applied
substitution
with
phenylsulfonyl
compounds
self-coulpings.
This
method
not
only
provides
a
new
approach
to
generation
intermediate
but
also
expands
application
boron
radicals.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 11, 2025
An
expedient
synthesis
of
α-aminoboronic
acid
derivatives
via
cobalt-catalyzed
remote
site-selective
hydroboration
unactivated
alkenes
is
described
herein.
The
strategy
characterized
by
its
simplicity,
site-selectivity,
and
wide
substrate
scope,
as
both
terminal
internal
could
undergo
the
reaction
smoothly,
affording
corresponding
products
in
good
yields.
According
to
mechanism,
Co-H
generated
from
Co(acac)2
presence
HBpin,
which
starts
chain-walking
a
series
alkene
insertion
β-H
elimination
process.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 18, 2025
Herein,
a
nickel-catalyzed,
photoredox
Giese
addition
reaction
with
readily
accessible
alkyl
bromides,
driven
by
available
feedstock
MeOH
as
the
halogen-atom
transfer
(XAT)
reagent,
was
successfully
achieved
under
mild
conditions.
The
versatility
of
this
protocol
demonstrated
through
range
structurally
varied
bromides
and
Giese-type
acceptors
moderate
to
good
yields.
Mechanistic
investigation
highlights
that
formation
radicals
XAT
tentatively
prompted
•CH2OH,
which
derived
from
sequential
photo-oxidation/1,2-hydrogen-atom
MeOH.