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 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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Heteroaromatic
alkylations
are
indispensable
reactions
for
synthesizing
biologically
active
molecules.
The
anti-Markovnikov
hydroarylation
of
olefins
using
heteroaryl
halides
furnishes
the
product
as
a
single
regioisomer;
however,
catalytic
variants
ineffective
at
controlling
stereochemical
outcome
these
reactions.
Here,
we
report
synergistic
photoenzymatic
flavin-dependent
"ene"-reductases
with
ruthenium
photoredox
catalysts.
Enzyme
homologues
were
identified,
which
provide
access
to
both
enantiomers
in
greater
than
80%
yield
up
99:1
er.
This
method
is
effective
styrenyl-
and
unactivated
alkenes,
highlighting
generality
this
approach.
highest
yielding
system
involves
carboxylated
photocatalyst
increased
affinity
enzyme.
work
expands
types
radical
intermediates
that
enzymes
can
use
stereoselective
intermolecular
coupling
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 24, 2024
Abstract
Repurposing
enzymes
to
catalyze
non‐natural
asymmetric
transformations
that
are
difficult
achieve
using
traditional
chemical
methods
is
of
significant
importance.
Although
radical
C−O
bond
formation
has
emerged
as
a
powerful
approach
for
constructing
oxygen‐containing
compounds,
controlling
the
stereochemistry
poses
great
challenge.
Here
we
present
development
dual
bio‐/photo‐catalytic
system
comprising
an
ene‐reductase
and
organic
dye
achieving
stereoselective
lactonizations.
By
integrating
directed
evolution
photoinduced
single
electron
oxidation,
repurposed
engineered
ene‐reductases
steer
formations
(one
hydrolactonizations
lactonization‐alkylations
while
two
bonds
lactonization‐oxygenations).
This
catalysis
gave
new
diverse
array
enantioenhanced
5‐
6‐membered
lactones
with
vicinal
stereocenters,
part
which
bears
quaternary
stereocenter
(up
99
%
enantiomeric
excess,
up
12.9
:
1
diastereomeric
ratio).
Detailed
mechanistic
studies,
including
computational
simulations,
uncovered
synergistic
effect
enzyme
externally
added
organophotoredox
catalyst
Rh6G.
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.
