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
ACS Catalysis,
Год журнала:
2024,
Номер
14(6), С. 4318 - 4328
Опубликована: Март 6, 2024
Sulfonyl
fluorides
have
found
increasing
applications
as
functional
molecules
in
chemistry
and
biology.
We
herein
report
a
copper-catalyzed
atom-economical
access
to
two
categories
of
sulfonyl
through
radical
relay
strategy
the
presence
an
SO2
surrogate.
The
aliphatic
C(sp3)–H
bond
N-fluoro-N-alkyl
sulfonamides
reacted
via
1,5-hydrogen
atom
transfer
(HAT)
process,
affording
alkanesulfonyl
with
proximal
amino
group.
On
other
hand,
utilizing
substrates
containing
proper
C═C
double
resulted
intramolecular
olefin
aminofluorosulfonylation,
allowing
synthesis
fluorosulfonyl-functionalized
pyrrolidines
piperidines
atom-transfer
addition
(ATRA).
Both
reaction
systems
proceeded
under
mild
conditions,
requiring
no
additional
fluorine
source.
Experimental
computational
studies
suggest
that
S–F
coupling
is
likely
achieved
radical-rebound
pathway.
By
taking
advantage
SuFEx
multifunctionality
products,
method
applicable
late-stage
modification
bioactive
compounds,
drug
ligation
chemistry,
organic
synthesis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12282 - 12296
Опубликована: Авг. 2, 2024
A
visible-light-photocatalyzed
hydrosulfonylation
of
unactivated
alkenes
with
symmetrical
disulfones
using
2,4,6-triisopropylthiophenol
as
a
hydrogen
atom
donor
(H-D)
has
been
developed.
Generation
two
sulfonyl
radicals
from
via
activation
visible
light
photocatalysis
is
involved.
Mechanistic
studies
rule
out
that
are
generated
disulfone
an
energy
transfer
mechanism
previously
found
for
lower
oxidation
state
sulfur–sulfur-based
reactants
(i.e.,
thiosulfonates
and
disulfides).
Instead,
mimic
process
occurs.
This
involves
photoinduced
electron
(PET)
oxidative
quenching
the
excited
photocatalyst
(*PC)
disulfone,
which
generates
radical
sulfinate
byproduct,
followed
by
reduction
oxidized
(PC•+)
this
byproduct
(SET)
generating
second
(PC).
The
reaction
can
be
performed
in
dimethyl
carbonate
at
room
temperature,
features
broad
functional
group
compatibility,
allows
easy
recycling
disulfide
provided
2,4,6-trisubstituted
thiophenol
used
H-D.
compared
state-of-the-art
green
metrics.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 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 Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
radical-mediated
sulfonylation
relay
of
alkyl
alkynes/alkenes
with
electron-deficient
alkenes
using
Na
2
S
O
4
as
a
linker
is
developed
to
synthesize
highly
selective
(
Z
)-vinyl
and
sulfones
under
metal-free
catalyzed
system.
Highly
functionalized
sulfone
containing
scaffolds
are
ubiquitous
and
attracting
increasing
interest
in
pharmaceutical
agrochemicals
owing
to
their
enhanced
activities.
Herein,
we
present
an
alternative
protocol
access
highly
substituted
sulfones
from
readily
accessible
olefin
feedstocks
sulfinate
salts
through
a
DABSO
enabled
anti-Markovnikov
hydrosulfonylation
process.
Notably,
the
practical
procedure
features
excellent
compatibility
with
various
susceptible
functional
groups
broad
substrate
scope
under
mild
operationally
simple
conditions.
Gram-scale
preparation,
post-functionalization
of
complex
molecules,
applications
synthesis
bioactive
compounds
underscore
potential
drug
discovery.
Abstract
A
convenient
and
sustainable
method
for
synthesizing
sulfonyl‐containing
compounds
through
a
catalyst‐free
aqueous‐phase
hydrosulfonylation
of
alkenes
alkynes
with
sulfonyl
chlorides
under
visible
light
irradiation
is
presented.
Unactivated
alkenes,
electron‐deficient
alkyl
aryl
can
be
hydrosulfonylated
various
at
room
temperature
excellent
yields
geometric
selectivities
by
using
tris(trimethylsilyl)silane
as
hydrogen
atom
donor
silyl
radical
precursor
to
activate
chlorides.
Mechanistic
studies
revealed
that
the
photolysis
in
aqueous
solution
produce
crucial
success
this
reaction.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(32), С. 6443 - 6484
Опубликована: Янв. 1, 2024
Alkynes
are
important
in
organic
synthesis.
This
review
mainly
focuses
on
the
recent
advances
(2013–2023)
alkynes
with
C–S
bond
formation,
based
more
than
30
kinds
of
sulfur
reagents.
