Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
This
study
describes
a
pioneering
visible-light-induced
phosphine-catalyzed
halogen-atom
transfer
(XAT)
strategy
that
heralds
new
era
in
the
difunctionalization
of
[1.1.1]propellane.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(34), P. 15871 - 15878
Published: Aug. 19, 2022
The
concurrent
installation
of
C-C
and
C-N
bonds
across
alkene
frameworks
represents
a
powerful
tool
to
prepare
motifs
that
are
ubiquitous
in
pharmaceuticals
bioactive
compounds.
To
construct
such
prevalent
bonds,
most
difunctionalization
methods
demand
the
use
precious
metals
or
activated
alkenes.
We
report
metal-free,
photochemically
mediated
imino-alkylation
electronically
diverse
alkenes
install
both
alkyl
iminyl
groups
highly
efficient
manner.
exceptionally
mild
reaction
conditions,
broad
substrate
scope,
excellent
functional
group
tolerance,
facile
one-pot
protocol
highlight
utility
this
method
privileged
from
readily
available
acid
feedstocks.
One
key
striking
feature
transformation
is
an
electrophilic
trifluoromethyl
radical
equally
with
electron-deficient
electron-rich
Additionally,
dispersion-corrected
density
theory
(DFT)
empirical
investigations
provide
detailed
mechanistic
insight
into
reaction.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(10), P. 4550 - 4558
Published: March 7, 2022
Transition-metal
catalysis
of
substitution
reactions
alkyl
electrophiles
by
nitrogen
nucleophiles
is
beginning
to
emerge
as
a
powerful
strategy
for
synthesizing
higher-order
amines,
well
controlling
their
stereochemistry.
Herein,
we
report
that
readily
accessible
chiral
copper
catalyst
(commercially
available
components)
can
achieve
the
photoinduced,
enantioconvergent
coupling
variety
racemic
tertiary
with
aniline
generate
new
C–N
bond
good
ee
at
fully
substituted
stereocenter
product;
whereas
this
copper-catalyzed
proceeds
−78
°C,
in
absence
light
and
catalyst,
virtually
no
formation
observed
even
upon
heating
80
°C.
The
mechanism
catalytic
process
has
been
interrogated
aid
wide
array
tools,
including
independent
synthesis
proposed
intermediates
reactivity
studies,
spectroscopic
investigations
featuring
photophysical
EPR
data,
DFT
calculations.
These
studies
led
identification
three
copper-based
cycle,
three-coordinate
formally
copper(II)–anilido
(DFT
analysis
points
its
formulation
copper(I)–anilidyl
radical)
complex
serves
persistent
radical
couples
organic
desired
enantioselectivity.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(4), P. 1986 - 1992
Published: Jan. 21, 2022
We
report
here
a
mechanistically
distinct
approach
to
achieve
Suzuki-Miyaura-type
cross-couplings
between
alkyl
iodides
and
aryl
organoborons.
This
process
requires
copper
catalyst
but,
in
contrast
with
previous
approaches
based
on
palladium
nickel
systems,
does
not
utilizes
the
metal
for
activation
of
electrophile.
Instead,
this
strategy
exploits
halogen-atom-transfer
ability
α-aminoalkyl
radicals
convert
secondary
into
corresponding
that
then
are
coupled
aryl,
vinyl,
alkynyl,
benzyl,
allyl
boronate
species.
These
novel
coupling
reactions
feature
simple
setup
conditions
(1
h
at
room
temperature)
facilitate
access
privileged
motifs
targeted
by
pharmaceutical
sector.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(30), P. 16630 - 16641
Published: July 24, 2023
β-(Hetero)arylethylamines
are
privileged
structural
motifs
found
in
many
high-value
organic
molecules,
including
pharmaceuticals
and
natural
products.
To
construct
these
important
molecular
skeletons,
previous
methods
mainly
achieved
by
amino(hetero)arylation
reaction
with
the
aid
of
transition
metals
preactivated
substrates.
Herein,
we
report
a
metal-free
photoinduced
intermolecular
for
single-step
installation
both
(hetero)aryl
iminyl
groups
across
alkenes
an
efficient
regioselective
manner.
This
method
shows
broad
scope
(up
to
124
examples)
excellent
tolerance
various
olefins─from
simplest
ethylene
complex
multisubstituted
can
all
participate
reaction.
Furthermore,
aminosulfonylation
be
also
conducted
presence
sodium
bisulfite
as
SO2
source.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(7), P. 4985 - 4991
Published: March 28, 2023
Here,
we
report
a
toolbox
strategy
to
cross-couple
unactivated
secondary
alkyl
iodides
with
various
N-,
O-,
and
C-based
nucleophiles.
This
harnesses
the
ability
of
photoredox-generated
phenyl
radicals
mediate
halogen-atom
transfer
(XAT)
convert
into
corresponding
radicals.
These
species
engage
in
second
catalytic
cycle,
mediated
by
copper,
which
enables
C–N/O/C
bond
formation
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
14(2), P. 619 - 627
Published: Dec. 28, 2023
Synthesis
of
bicyclo[1.1.1]pentane
(BCP)
heteroaryls
continues
to
be
a
part
the
most
important
tasks
in
organic
synthesis
because
they
are
significant
class
bioisosteres
with
universal
applications
drug
discovery.
However,
substrate
scope
current
multicomponent
reactions
is
limited
tertiary
alkyl
radicals
and
prefunctionalized
(het)arenes
due
their
intrinsic
mechanisms,
resulting
decrease
application
value.
Herein,
we
report
straightforward
alternative
for
(halo)alkyl
BCP-heteroaryls
from
[1.1.1]propellane
enabled
by
α-aminoalkyl
radical-mediated
halogen-atom
transfer
(XAT).
Carbon
derived
commonly
available
precursors
such
as
primary,
secondary,
halides
polyhalides
perform
additions
onto
give
BCP
radicals,
which
then
engage
C–H/C–C
couplings
different
heteroarenes.
A
wide
range
easily
constructed
moderate-to-good
yields.
Late-stage
functionalization
performed
on
approved
derivatives
proceeds
good
efficiency
produce
corresponding
BCP-heteroaryls.
The
control
experiments
density
functional
theory
(DFT)
calculations
reveal
radical
nature
reaction.
This
approach
not
only
verifies
(XAT)
strategy
but
also
provides
practical
efficient
route
multifunctionalized
BCPs,
significantly
expands
BCP-heteroaryl-type
development.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 7922 - 7930
Published: March 18, 2024
Chromoselective
bond
activation
has
been
achieved
in
organic
helicenium
(nPr-DMQA+)-based
photoredox
catalysis.
Consequently,
control
over
chromoselective
C(sp2)–X
multihalogenated
aromatics
demonstrated.
nPr-DMQA+
can
only
initiate
the
halogen
atom
transfer
(XAT)
pathway
under
red
light
irradiation
to
activate
low-energy-accessible
C(sp2)–I
bonds.
In
contrast,
blue
initiates
consecutive
photoinduced
electron
(conPET)
more
challenging
C(sp2)–Br
Comparative
reaction
outcomes
have
demonstrated
α-arylation
of
cyclic
ketones
with
and
lights.
Furthermore,
red-light-mediated
selective
bonds
activated
iodobromoarenes
keep
bromo
functional
handle
untouched.
Finally,
strength
catalysis
highlighted
two-fold
functionalization
using
both
photo-to-transition
metal
photo-to-photocatalyzed
transformations.
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.