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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(32), P. 22424 - 22430
Published: Aug. 1, 2024
Amide
alkylation
is
a
fundamental
process
in
organic
chemistry.
However,
the
low
nucleophilicity
of
amides
means
that
divergent
coupling
with
alkyl
electrophiles
often
not
achievable.
To
circumvent
this
reactivity
challenge,
individual
amine
synthesis
followed
by
amidation
standard
agents
generally
required.
Herein,
we
demonstrate
radical
solution
to
challenge
using
an
amine–borane
complex
and
copper
catalysis
under
oxidative
conditions.
While
borohydride
reagents
are
used
as
reducing
ionic
chemistry,
their
conversion
into
amine-ligated
boryl
radicals
diverts
toward
halogen-atom
transfer.
This
enables
halides
corresponding
for
amide
functionalization
via
catalysis.
The
applicable
N-alkylation
primary
employing
unactivated
iodides
bromides,
it
was
also
showcased
late-state
both
amide-
halide-containing
drugs.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(11), P. 7791 - 7802
Published: March 10, 2024
The
development
of
new
synthetic
methods
for
B–H
bond
activation
has
been
an
important
research
area
in
boron
cluster
chemistry,
which
may
provide
opportunities
to
broaden
the
application
scope
clusters.
Herein,
we
present
a
reaction
strategy
direct
site-selective
functionalization
nido-carboranes
initiated
by
photoinduced
cage
via
noncovalent
cage···π
interaction.
As
result,
nido-carborane
radical
is
generated
through
single
electron
transfer
from
3D
2D
photocatalyst
upon
irradiation
with
green
light.
resulting
transient
could
be
directly
probed
advanced
time-resolved
EPR
technique.
In
air,
subsequent
transformations
active
have
led
efficient
and
selective
B–N,
B–S,
B–Se
couplings
presence
N-heterocycles,
imines,
thioethers,
thioamides,
selenium
ethers.
This
protocol
also
facilitates
both
late-stage
modification
drugs
synthesis
nido-carborane-based
drug
candidates
neutron
capture
therapy
(BNCT).
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(33), P. 22874 - 22880
Published: Aug. 2, 2024
A
novel
reactivity
toward
C-F
bond
functionalization
has
been
developed,
which
could
be
designated
as
fluorine
atom
transfer
(FAT).
photoexcited
state
of
an
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(9), P. 3060 - 3070
Published: Jan. 1, 2024
Boryls
and
their
compounds
are
important
due
to
diverse
range
of
applications
in
the
fields
materials
science
catalysis.
They
an
integral
part
boron
chemistry,
which
has
attracted
tremendous
research
interest
over
past
few
decades.
In
this
perspective,
we
provide
in-depth
analysis
reaction
chemistry
boryl
from
a
structure
bonding
perspective.
We
discuss
reactivity
boryls
various
transition
metal
complexes
diborane(4)
towards
different
substrate
molecules,
with
focus
on
nucleophilic
electrophilic
properties
processes.
Additionally,
briefly
radicals.
Our
sheds
new
light
unique
potential
for
catalytic
applications.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 11, 2025
Boron
compounds
are
widely
employed
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Among
them,
borylated
heterocycles
serve
as
versatile
synthons
for
the
construction
of
new
C-C
or
C-heteroatom
bonds
via
coupling
radical
processes.
Such
methods
direct
C-H
borylation
reactions
high
synthetic
value
to
reduce
number
steps
amount
waste
improve
efficiency.
Despite
significant
advances,
remains
an
ongoing
challenge
with
great
potential
applications
chemical
synthesis.
Herein,
we
describe
a
photocatalytic
reaction
five-membered
ring
by
employing
stable
N-heterocyclic
carbene
borane
borylating
reagent
photoredox
catalyst.
Under
green
mild
conditions,
was
achieved
on
series
benzo-fused
heterocyclic
compounds.
Further
studies
demonstrate
utility
this
approach
pharmaceutical
agrochemical
research.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Oct. 26, 2023
Abstract
Alkyl
halides,
widely
recognized
as
important
building
blocks
and
reagents
in
organic
synthesis,
can
serve
versatile
alkyl
radical
precursors
radical-based
transformations.
However,
generating
radicals
directly
from
unactivated
halides
under
mild
conditions
remains
a
challenge
due
to
their
extremely
low
reduction
potentials.
To
address
this
issue,
α-aminoalkyl
were
employed
efficient
halogen-atom
transfer
(XAT)
the
photoredox
activation
of
halides.
Here,
we
report
an
effective
electrooxidation
strategy
for
iodides
via
electrochemical
(
e
-XAT)
process
conditions.
The
generated
by
anodic
oxidation
are
demonstrated
be
XAT
these
This
facile
electricity-driven
obviates
need
sacrificial
anodes
external
chemical
oxidants.
method
successfully
applies
wide
variety
iodides,
including
primary,
secondary,
tertiary,
well
structurally
diverse
olefins,
exhibiting
excellent
functional
group
tolerance.
Moreover,
further
demonstrate
utility
rapidly
functionalizing
complex
molecules
biomolecules.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 15, 2024
Herein,
we
describe
a
general
hydrodefunctionalization
protocol
of
alcohols
and
amines
through
common
isonitrile
intermediate.
To
cleave
the
relatively
inert
C-NC
bond,
leveraged
dual
hydrogen
atom
transfer
(HAT)
photoredox
catalysis
to
generate
nucleophilic
boryl
radical,
which
readily
forms
an
imidoyl
radical
intermediate
from
isonitrile.
Rapid
β-scission
then
accomplishes
defunctionalization.
This
method
has
been
applied
both
amine
alcohol-containing
pharmaceuticals,
natural
products,
biomolecules.
We
extended
this
approach
reduction
carbonyls
olefins
their
saturated
counterparts,
as
well
hydrodecyanation
alkyl
nitriles.
Both
experimental
computational
studies
demonstrate
facile
reconcile
differences
in
reactivity
between
nitriles
isonitriles
within
our
protocol.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5839 - 5843
Published: July 1, 2024
Light-mediated
Halogen-Atom
Transfer
(XAT)
has
become
a
significant
methodology
in
contemporary
synthesis.
Unlike
α-aminoalkyl
and
silyl
radicals,
ligated
boryl
radicals
(LBRs)
have
not
been
extensively
explored
as
halogen
atom
abstractors.
In
this
study,
we
introduce
NHC-ligated
boranes
optimal
radical
chain
carriers
for
the
intermolecular
reductive
hydroalkylation
hydroarylation
of
electron-deficient
olefins
by
using
direct
UV-A
light
irradiation.
DFT
analysis
allowed
us
to
rationalize
critical
role
NHC
ligand
facilitating
efficient
propagation.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(17), P. 12658 - 12667
Published: Aug. 19, 2024
Nickel/photoredox
catalysis
has
emerged
as
a
powerful
platform
for
exploring
nontraditional
and
challenging
cross-couplings.
Herein,
metallaphotoredox
catalytic
protocol
been
developed
on
the
basis
of
tertiary
amine-ligated
boryl
radical-induced
halogen
atom
transfer
process
under
blue-light
irradiation.
A
wide
variety
aryl
heteroaryl
bromides
featuring
different
functional
groups
pharmaceutical
moieties
were
facilely
coupled
to
rapidly
install
C(sp3)-enriched
aromatic
scaffolds.
The
compatibility
Lewis
base-ligated
borane
with
nickel
was
well
exemplified
extend
chemical
space
Ni-catalyzed
cross-electrophile
coupling.
