Organic Letters,
Год журнала:
2022,
Номер
24(43), С. 8019 - 8024
Опубликована: Окт. 20, 2022
The
modular
cyanoalkylamination
of
alkenes
using
bench-stable
and
easy-to-handle
α-imino-oxy
acid
oxime
esters
as
difunctional
reagents
creates
new
synthetic
avenues.
A
metal-free
photosensitization
protocol
for
the
installation
both
amino
cyanoalkyl
functionalities
onto
alkene
feedstocks
in
a
single
step
via
two
differently
reactive
nitrogen-centered
radicals
was
developed
energy-transfer
catalysis.
Excellent
functional
group
tolerance
mild
reaction
conditions
also
render
this
suitable
pharmaceutically
relevant
molecule-derived
alkenes.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(5), С. 1723 - 1772
Опубликована: Янв. 1, 2023
Defective
two-dimensional
(2D)
materials
show
huge
potential
for
energy-related
fields.
This
review
overviews
the
formation/evolution
mechanisms
and
engineering
strategies
of
defects
in
2D
materials,
which
enable
enhanced
electrode
reaction
kinetics.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(3), С. 1068 - 1089
Опубликована: Янв. 1, 2024
Leveraging
light
energy
to
expose
the
‘dark’
reactive
states
describes
whole
essence
of
triplet–triplet
transfer.
This
offers
an
impressive
opportunity
conduct
a
multitude
diverse
reactions
and
access
sought-after
molecular
motifs.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16630 - 16641
Опубликована: Июль 24, 2023
β-(Hetero)arylethylamines
are
privileged
structural
motifs
found
in
many
high-value
organic
molecules,
including
pharmaceuticals
and
natural
products.
To
construct
these
important
molecular
skeletons,
previous
methods
mainly
achieved
by
amino(hetero)arylation
reaction
with
the
aid
of
transition
metals
preactivated
substrates.
Herein,
we
report
a
metal-free
photoinduced
intermolecular
for
single-step
installation
both
(hetero)aryl
iminyl
groups
across
alkenes
an
efficient
regioselective
manner.
This
method
shows
broad
scope
(up
to
124
examples)
excellent
tolerance
various
olefins─from
simplest
ethylene
complex
multisubstituted
can
all
participate
reaction.
Furthermore,
aminosulfonylation
be
also
conducted
presence
sodium
bisulfite
as
SO2
source.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(18), С. 9378 - 9418
Опубликована: Янв. 1, 2024
Organic
transformation
by
light-driven
catalysis,
especially,
photocatalysis
and
photothermal
denoted
as
photo(thermal)
is
an
efficient,
green,
economical
route
to
produce
value-added
compounds.
In
recent
years,
owing
their
diverse
structure
types,
tunable
pore
sizes,
abundant
active
sites,
metal-organic
framework
(MOF)-based
catalysis
has
attracted
broad
interest
in
organic
transformations.
this
review,
we
provide
a
comprehensive
systematic
overview
of
MOF-based
for
First,
the
general
mechanisms,
unique
advantages,
strategies
improve
performance
MOFs
are
discussed.
Then,
outstanding
examples
transformations
over
introduced
according
reaction
type.
addition,
several
representative
advanced
characterization
techniques
used
revealing
charge
kinetics
intermediates
presented.
Finally,
prospects
challenges
field
proposed.
This
review
aims
inspire
rational
design
development
materials
with
improved
catalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(15), С. 10899 - 10907
Опубликована: Апрель 3, 2024
In
the
long-standing
quest
to
synthesize
fundamental
building
blocks
with
key
functional
group
motifs,
photochemistry
in
recent
past
has
comprehensively
established
its
attractiveness.
Amino
alcohols
are
not
only
functionally
diverse
but
ubiquitous
biologically
active
realm
of
compounds.
We
developed
bench-stable
bifunctional
reagents
that
could
then
access
sparsely
reported
γ-amino
directly
from
feedstock
alkenes
through
energy
transfer
(EnT)
photocatalysis.
A
designed
1,3-linkage
across
is
made
possible
by
intervention
a
radical
Brook
rearrangement
takes
place
downstream
EnT-mediated
homolysis
our
reagent(s).
combination
experimental
mechanistic
investigations
and
detailed
computational
studies
(DFT)
indicates
chain
propagated
reaction
pathway.
We
describe
an
efficient
acyl
esterification
method
for
alkenes
utilizing
acyloxime
esters
as
bifunctional
reagents
featuring
radical
acylation
and
congested
C–O
bond
formation.
This
approach
is
characterized
by
mild
photoredox
conditions,
high
step
atom
economy,
a
broad
substrate
scope,
excellent
regioselectivity.
A
variety
of
valuable
α-acyl
hindered
alcohol
esters,
including
those
obtained
via
gram-scale
synthesis
late-stage
functionalization
pharmaceutical
molecules,
were
presented,
demonstrating
its
synthetic
potential
practicability.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1854 - 1941
Опубликована: Янв. 17, 2025
Over
the
past
decade,
visible-light-mediated
energy-transfer
(EnT)
catalysis,
particularly
triplet–triplet
(TTEnT)
has
emerged
as
a
mild
and
environmentally
friendly
approach
for
diverse
organic
synthetic
transformations.
In
contrast
to
photoredox
which
typically
requires
sacrificial
electron
donors
or
acceptors
complete
catalytic
cycle,
EnT
photocatalysis
generally
proceeds
with
high
atom
economy
while
minimizing
generation
of
wasteful
byproducts.
Furthermore,
successful
catalysis
is
contingent
upon
precise
control
redox
potentials
both
photocatalysts
substrates,
strategies
are
primarily
influenced
by
triplet
energy
compatibility
between
these
entities.
Considering
growing
importance
photocatalysis,
well
hydrofunctionalization
difunctionalization
reactions
in
synthesis,
this
review
systematically
summarizes
significant
advancements
EnT-enabled
unsaturated
compounds
via
sigma-bond
homolysis
over
decade.
Special
emphasis
placed
on
elucidating
substrate
scopes
mechanistic
scenarios.
Additionally,
discusses
versatile
applications
methodologies
addresses
current
challenges
opportunities
within
evolving
research
field.
This
structured
into
six
main
categories
based
different
types
sigma-bonds
undergoing
homolysis.
These
include
transformations
mediated
1)
N–O
bond
oxime
esters
other
N,O-radical
precursors;
2)
N–S
N-sulfonyl
imines
N,S-radical
3)
chalcogen–chalcogen
disulfides
oxy/thio/selenosulfonates;
4)
C–S
tri/difluoromethylated
sulfinates,
acetylenic
triflones,
arylsulfonium
salts;
5)
C–X
(X
=
halogen)
halides;
6)
acceptors.
Through
providing
theoretical
backgrounds
along
comprehensive
overview
currently
employed
acceptors,
photosensitizers,
contemporary
EnT-induced
compounds,
aims
serve
an
invaluable
resource
future
innovations
rapidly
ACS Catalysis,
Год журнала:
2023,
Номер
13(14), С. 9806 - 9816
Опубликована: Июль 11, 2023
Cyclopropanes
bearing
contiguous
all-carbon
quaternary
centers
continue
to
attract
attention
due
their
bioactivities.
However,
methods
obtain
cyclopropanes
with
remain
largely
unexplored
the
high
steric
hindrance
of
these
compounds.
Herein,
we
report
a
visible-light-mediated
energy-transfer
(EnT)
strategy
realize
in
situ
donor/donor
carbenes
from
readily
available
N-tosylhydrazones,
facilitating
synthesis
highly
congested
EWG-free
cyclopropanes.
Through
this
approach,
are
rapidly
installed
into
complex
bioactive
molecules,
fluorescent
and
other
useful
building
blocks
that
challenging
synthesize.
Detailed
mechanistic
reactions
DFT
studies
clearly
demonstrated
role
photosensitizer,
formation
carbenes,
necessity
light
base
system.
