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
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(27)
Published: April 24, 2024
Abstract
Positron
emission
tomography
(PET)
is
becoming
increasingly
important
in
nuclear
medicine
and
drug
discovery.
To
date,
the
development
of
many
potential
PET
tracers
hampered
by
lack
suitable
synthetic
pathways
for
their
preparation.
This
particularly
true
highly
desired
radiolabeling
compounds
bearing
[
18
F]CF
3
‐groups.
For
instance,
S(O)
n
CF
‐groups
(
=0,
1,
2)
serve
as
structural
motif
a
range
biologically
active
compounds,
but
radiosynthesis
remains
largely
unprecedented
(for
=1,
2).
Herein,
we
describe
general
methods
F‐labeled
aryl
trifluoromethyl
sulfones,
‐sulfoxides,
‐sulfides.
All
three
are
operationally
straightforward,
start
from
widely
available
precursors,
i.e.,
sulfonyl
fluorides
thiophenols,
make
use
recently
established
F]Ruppert‐Prakash
reagent.
Further,
syntheses
display
good
functional
group
tolerance
demonstrated
F‐labeling
more
than
40
compounds.
The
applicability
new
method
bioactive
molecules,
optionally
to
be
used
tracers.
In
broader
context,
this
work
presents
substantial
expansion
chemical
space
radiofluorinated
motifs
Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 21, 2024
Abstract
Sulfonyl
fluorides,
due
to
their
balanced
potential
reactivity
and
stability
as
well
compatibility
with
biological
systems,
have
become
important
synthetic
intermediates
building
blocks
in
the
fields
of
organic
synthesis,
drug
discovery,
materials
science.
Especially
after
report
sulfur(VI)
fluoride
exchange
(SuFEx)
chemistry
by
Sharpless
others,
research
on
sulfonyl
compounds
related
has
increased
significantly.
This
review
summarizes
application
fluorides
synthesis
period
2014–2024,
discussing
different
types
reactions,
including
C–X
bond
formation
(including
C–C,
C–N,
C–F
etc.),
S–C
formation,
S–N
S–O
multicomponent
‘one-pot’
cyclization.
1
Introduction
2
Fluorides
Applied
(C,
N,
F)
Bond
Formation
3
4
5
6
Multicomponent
Reactions
7
Cyclizations
8
Conclusion
Perspective
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:
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
