Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 16, 2024
A
visible-light-induced
method
for
the
hydrodichloromethylation
of
unactivated
alkenes
using
chloroform
(CHCl3)
was
developed,
employing
pyridine·BH3
as
halogen
atom
transfer
(XAT)
reagent.
The
strategy
showed
a
broad
functional
group
tolerance,
and
29
examples
alkenes,
including
complex
natural
products
or
drug
derivatives,
have
been
established
with
good
yields.
Mechanistic
studies
indicated
that
CHCl3
serves
both
source
dichloromethyl
radical
hydrogen
(HAT)
reagent,
borane
short-chain
reaction
process
involved
in
this
system.
This
represents
novel
approach
without
an
additional
HAT
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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 30, 2024
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.
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.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 6, 2024
Abstract
A
visible‐light‐induced
radical
tandem
difluoroalkylation/cyclization
to
construct
CF
2
‐containing
isoquinolinonedione
skeletons
with
methacryloyl
benzamides
is
developed.
Broad
substrate
scopes
are
compatible
metal‐,
oxidant‐
and
photocatalyst‐free
conditions
under
room
temperature
in
good‐to‐excellent
yields.
Mechanistic
analysis
revealed
that
the
transformation
initiated
by
photoinduced
electron
donor‐acceptor
(EDA)
complexes
formation.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
31(8)
Published: Nov. 13, 2024
The
advanced
strategy
using
Lewis
base-boryl
radicals
(LBRs)
has
recently
been
proposed
for
the
addition
of
alkyl
substituents
to
full-carbon
quaternary
center
an
organic
molecule.
However,
as
rate-determining
step
in
whole
route,
reaction
rate
constants
LBRs
with
substrates
are
extremely
lacking.
In
this
paper,
4-dimethylaminopyridine
(DMAP)-BH2⋅
was
selected
a
representative
LBRs,
and
its
reactions
six
monochloro-substituted
substrates,
including
three
methyl
chlorobenzoates
chlorinated
acetanilides
were
studied
experiments
theoretical
calculations.
bimolecular
constants,
kq,
determined
laser
flash
photolysis
approach.
By
comparing
activation
energies
along
two
pathways,
we
have
clarified
attacking
carbonyl
oxygen
instead
chlorine
atom.
Furthermore,
noncovalent
interaction
(NCI)
analyses
on
these
indicate
that
weak
interactions,
such
hydrogen-bonding
van
der
Waals
significant
influence
reactivity
substrates.
Our
study
provides
concrete
clues
extend
synthetic
strategy.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 16, 2024
A
visible-light-induced
method
for
the
hydrodichloromethylation
of
unactivated
alkenes
using
chloroform
(CHCl3)
was
developed,
employing
pyridine·BH3
as
halogen
atom
transfer
(XAT)
reagent.
The
strategy
showed
a
broad
functional
group
tolerance,
and
29
examples
alkenes,
including
complex
natural
products
or
drug
derivatives,
have
been
established
with
good
yields.
Mechanistic
studies
indicated
that
CHCl3
serves
both
source
dichloromethyl
radical
hydrogen
(HAT)
reagent,
borane
short-chain
reaction
process
involved
in
this
system.
This
represents
novel
approach
without
an
additional
HAT
