Journal of the American Chemical Society,
Год журнала:
2021,
Номер
144(1), С. 145 - 152
Опубликована: Дек. 30, 2021
The
positional
isomerization
of
C═C
double
bonds
is
a
powerful
strategy
for
the
interconversion
alkene
regioisomers.
However,
existing
methods
provide
access
to
thermodynamically
more
stable
isomers
from
less
starting
materials.
Here,
we
report
discovery
dual
catalyst
system
that
promotes
contra-thermodynamic
under
photochemical
irradiation,
providing
terminal
directly
conjugated,
internal
utility
method
demonstrated
in
deconjugation
diverse
electron-rich/electron-poor
alkenes
and
through
strategic
application
natural
product
synthesis.
Mechanistic
studies
are
consistent
with
regiospecific
bimolecular
homolytic
substitution
(SH2′)
mechanism
proceeding
an
allyl-cobaloxime
intermediate.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(6), С. 4026 - 4035
Опубликована: Фев. 1, 2024
Herein,
we
report
a
divergent
synthesis
of
fluoroalkyl
ketones
through
visible-light-induced
reactions
between
readily
available
organoboronic
esters
and
acylsilanes.
Selective
control
the
reactivity
in
situ
generated
organoboronate
complexes
is
key
to
achieving
transformations.
Under
basic
conditions,
undergo
deboronative
fluoride
elimination,
resulting
formation
enol
silyl
ethers
as
intermediates
that
react
with
various
electrophiles
generate
defluorinated
products.
Moreover,
combination
peroxide,
1,2-shift
group
favored
over
elimination
ketal
intermediates,
leading
This
transition-metal-free
reaction
operationally
simple,
aryl,
alkenyl,
alkyl
boronic
are
all
suitable
substrates.
The
synthetic
potential
has
been
demonstrated
by
gram-scale
facile
bioactive
molecules
including
zifrosilone
its
analogs.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(14), С. 10142 - 10149
Опубликована: Март 27, 2024
Saturated
bicyclic
compounds
make
up
a
valuable
class
of
building
blocks
in
the
development
agrochemicals
and
pharmaceuticals.
Here,
we
present
synthesis
borylated
bicyclo[2.1.1]hexanes
via
crossed
[2
+
2]-cycloaddition.
Due
to
presence
C–B
bond,
variety
structures
can
be
easily
prepared
that
are
not
accessible
by
other
methods.
Moreover,
rare
photo-ene
reaction
is
also
disclosed,
allowing
for
diastereoselective
trisubstituted
cyclopentanes.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18210 - 18217
Опубликована: Май 24, 2024
Molecular
rearrangement
occupies
a
pivotal
position
among
fundamental
transformations
in
synthetic
chemistry.
Radical
translocation
has
emerged
as
prevalent
tool,
efficiently
facilitating
the
migration
of
diverse
functional
groups.
In
contrast,
development
di-π-methane
remains
limited,
particularly
terms
cyano
This
is
primarily
attributed
to
energetically
unfavorable
three-membered-ring
transition
state.
Herein,
we
introduce
an
unprecedented
di-π-ethane
enabled
by
energy-transfer
catalysis
under
visible
light
conditions.
innovative
open-shell
boasts
broad
tolerance
toward
range
groups,
encompassing
even
complex
drug
and
natural
product
derivatives.
Overall,
reported
represents
complementary
strategy
radical
catalysis.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 16, 2024
Abstract
The
past
century
has
witnessed
a
large
number
of
reports
on
the
Z
/
E
isomerization
alkenes.
However,
vast
majority
them
are
still
limited
to
di-
and
tri-substituted
stereospecific
tetrasubstituted
alkenes
remains
be
an
underdeveloped
area,
thus
lacking
in
stereodivergent
synthesis
axially
chiral
Herein
we
report
atroposelective
alkene
analogues
by
asymmetric
allylic
substitution-isomerization,
followed
their
via
triplet
energy
transfer
photocatalysis.
In
this
regard,
N
-vinylquinolinones
is
achieved
efficiently.
Mechanistic
studies
indicate
that
benzylic
radical
generation
distribution
two
key
factors
for
preserving
enantioselectivities
compounds.
JACS Au,
Год журнала:
2024,
Номер
4(8), С. 2746 - 2766
Опубликована: Авг. 8, 2024
Photocatalysis
is
a
versatile
and
rapidly
developing
field
with
applications
spanning
artificial
photosynthesis,
photo-biocatalysis,
photoredox
catalysis
in
solution
or
supramolecular
structures,
utilization
of
abundant
metals
organocatalysts,
sustainable
synthesis,
plastic
degradation.
In
this
Perspective,
we
summarize
conclusions
from
an
interdisciplinary
workshop
young
principal
investigators
held
at
the
Lorentz
Center
Leiden
March
2023.
We
explore
how
diverse
fields
within
photocatalysis
can
benefit
one
another.
delve
into
intricate
interplay
between
these
subdisciplines,
by
highlighting
unique
challenges
opportunities
presented
each
multidisciplinary
approach
drive
innovation
lead
to
solutions
for
future.
Advanced
collaboration
knowledge
exchange
across
domains
further
enhance
potential
photocatalysis.
Artificial
photosynthesis
has
become
promising
technology
solar
fuel
generation,
instance,
via
water
splitting
CO
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 7, 2025
Considering
the
unique
electronic
properties
of
CF2
and
CN
groups,
CF2CN
group
has
significant
potential
in
drug
agrochemical
development,
as
well
material
sciences.
However,
incorporating
a
remains
considerable
challenge.
In
this
work,
we
disclose
use
bromodifluoroacetonitrile
(BrCF2CN),
cost-effective
readily
available
reagent,
radical
source
for
cyanodifluoromethylation
alkyl
alkenes,
aryl
alkynes,
(hetero)arenes
under
photocatalytic
conditions.
This
protocol
demonstrates
an
exceptionally
broad
substrate
scope
remarkable
tolerance
to
various
functional
groups.
Notably,
alkynes
predominantly
provides
sterically
hindered
thermodynamically
unfavorable
outcome,
(hetero)arene
C-H
bonds
are
directly
amenable
without
pre-functionalization.
Here,
authors
report
(BrCF2CN)
ACS Catalysis,
Год журнала:
2021,
Номер
11(21), С. 13567 - 13574
Опубликована: Окт. 25, 2021
The
enantio-
and
stereoselective
synthesis
of
stereodefined
alkenes,
especially
the
functionalized
Z-isomer
with
an
allylic
stereogenic
center,
remains
a
great
challenge.
We
herein
report
enantioselective
benzylic
C(sp3)–H
alkenylation
simple
alkylarenes
vinyl
bromides
via
photoinduced
nickel
catalysis,
which
allows
for
stereodivergent
both
enantioenriched
Z-
E-alkenes
bearing
aryl-substituted,
tertiary
centers.
Interestingly,
tunable
Z/E-selectivity
is
achieved
by
energy
transfer
catalysis
judicious
choice
photocatalyst
counteranion.
This
versatile
strategy
features
starting
materials,
mild
reaction
conditions,
broad
substrate
scope,
divergent
E-selectivity,
high
enantioselectivities.
Moreover,
formal
asymmetric
alkylation
can
also
be
one-pot
alkenylation/reduction
sequence,
providing
complementary
to
address
notoriously
challenging
stereochemical
control
in
C(sp3)–C(sp3)
bond
construction.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(23), С. 10133 - 10138
Опубликована: Июнь 6, 2022
A
visible-light-mediated,
enantioselective
approach
to
axially
chiral
alkenes
is
described.
Starting
from
a
racemic
mixture,
major
alkene
enantiomer
formed
due
selective
triplet
energy
transfer
catalytically
active
sensitizer.
catalyst
loading
of
2
mol
%
was
sufficient
guarantee
consistently
high
enantioselectivities
and
yields
(16
examples,
51%-quant.,
81–96%
ee).
NMR
studies
DFT
computations
revealed
that
more
rapid
within
the
substrate–catalyst
complex
minor
enantiomer.
Since
this
continuously
racemized,
enriched
in
photostationary
state.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Июнь 18, 2022
Sulfonyl
fluorides
are
key
components
in
the
fields
of
chemical
biology,
materials
science
and
drug
discovery.
In
this
line,
highly
active
SO2F
radical
has
been
employed
for
construction
sulfonyl
fluorides,
but
utilization
gaseous
ClSO2F
as
precursor
is
limited
due
to
tedious
hazardous
preparation.
Meanwhile,
synthesis
from
inert
SO2F2
gas
through
a
fluorosulfonyl
(·SO2F)
process
met
with
inevitable
difficulties
high
homolytic
bond
dissociation
energy
S(VI)-F
bond.
Here
we
report
fluorosulfonylation
strategy
stereoselective
alkenyl
functional
alkyl
an
air-stable
crystalline
benzimidazolium
fluorosulfonate
cationic
salt
reagent.
This
bench-stable
redox-active
reagent
offers
useful
operational
protocol
unsaturated
hydrocarbons
good
yield
stereoselectivity,
which
can
be
further
transformed
into
valuable
moieties.
