Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 30, 2025
Epoxides
are
significant
chemicals
that
utilized
across
various
fields.
Here,
we
describe
an
unprecedented
photochemical
rearrangement
approach
for
synthesizing
a
diverse
collection
of
epoxides
enabled
by
energy
transfer
catalysis
under
visible
light
conditions.
The
process
enables
the
easy
preparation
α-amino-substituted
epoxide
derivatives
with
broad
substrate
scope,
functional
group
tolerance,
and
mild
reaction
Furthermore,
this
photorearrangement
has
also
been
applied
in
complex
architectures,
could
be
easily
transferred
to
amino
alcohol
derivatives.
Overall,
oxa-π,
σ-methane
provides
complementary
strategy
existing
methods
through
catalysis.
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.
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.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5122 - 5129
Опубликована: Янв. 1, 2024
This
study
demonstrates
a
strategy
involving
photoinduced
energy
transfer
for
decarboxylative
Minisci
C–H
(amino)alkylation
of
heteroarenes
employing
diverse
oxime
esters
(from
carboxylic
acids)
as
(amino)alkylating
reagents.
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
Organic Letters,
Год журнала:
2023,
Номер
25(10), С. 1742 - 1747
Опубликована: Март 8, 2023
A
new
class
of
iminosulfonylation
reagents
were
developed
and
extensively
used
in
the
1,2-iminosulfonylation
various
olefins.
Olefins
containing
bioactive
molecules,
such
as
indomethacin,
gemfibrozil,
clofibrate,
fenbufen,
afforded
desired
products
synthetically
useful
yields.
Furthermore,
first
remote
1,6-iminosulfonylation
alkenes
was
realized
by
using
oxime
ester
bifunctionalization
reagents.
Overall,
more
than
40
structurally
diverse
β-imine
sulfones
obtained
moderate
to
excellent
Organic Letters,
Год журнала:
2023,
Номер
25(10), С. 1782 - 1786
Опубликована: Март 8, 2023
A
metal-free
photosensitized
three-component
reaction
of
oxime
esters,
alkenes,
and
DABCO·(SO2)2
was
developed.
This
protocol
could
accommodate
a
wide
substrate
scope,
including
activated
unactivated
alkenes
aryl
aliphatic
carboxylic
acid
delivering
broad
range
β-amino
sulfones
in
moderate
to
high
yields.
The
insertion
SO2
as
linker
moiety
allows
the
manipulation
functionality
process,
expanding
utility
esters
bifunctional
reagents.
Organic Letters,
Год журнала:
2023,
Номер
25(12), С. 2129 - 2133
Опубликована: Март 21, 2023
Herein,
we
disclose
a
facile
and
versatile
trifluoromethylimination
of
alkene
with
rationally
designed
N-(diphenylmethylene)-1,1,1-trifluoromethanesulfonamide
as
bench-stable
readily
accessible
carboamination
reagent.
Enabled
by
an
energy
transfer
(EnT)
process,
array
alkenes
were
able
to
be
facilely
CF3-iminated
under
metal-free
photocatalytic
conditions.
The
mild
reaction
conditions
good
functional
group
compatibility
render
this
protocol
highly
valuable
for
the
difunctionalization
olefins
structural
complexity
diversity.
Organic Letters,
Год журнала:
2023,
Номер
25(13), С. 2349 - 2354
Опубликована: Март 27, 2023
An
organo-photocatalytic
sulfonylimination
of
alkenes
was
developed
by
employing
readily
available
N-sulfonyl
ketimines
as
bifunctional
reagents.
This
transformation,
featuring
prominent
functional
group
tolerance,
provides
a
direct
and
atom-economic
approach
for
the
synthesis
valuable
β-amino
sulfone
derivatives
single
regioisomer.
In
addition
to
terminal
alkenes,
internal
participate
in
this
reaction
with
high
diastereoselectivity.
N-Sulfonyl
aryl
or
alkyl
substituents
were
found
be
compatible
condition.
method
could
applied
late-stage
modifications
drugs.
Additionally,
formal
insertion
alkene
into
cyclic
sulfonyl
imine
observed,
affording
ring
expansion
product.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(43), С. 23814 - 23823
Опубликована: Окт. 18, 2023
Radical
remote
1,n-difunctionalization
reactions
(n
>
2)
of
alkenes
are
powerful
tools
to
efficiently
introduce
functional
groups
with
selected
distances
into
target
molecules.
Among
these
reactions,
1,5-difunctionalizations
an
important
subclass,
leading
sought-after
scaffolds,
but
typically
suffer
from
tailored
starting
materials
and
strict
limitations
for
the
formed
group
in
2-position.
Seeking
address
issues
make
radical
more
applicable,
we
report
a
novel
three-component
1,2,5-trifunctionalization
reaction
between
imine-based
bifunctional
reagents
two
distinct
alkenes,
driven
by
visible
light
energy
transfer-catalysis.
Key
achieving
this
selective
one-step
installation
three
different
via
choreographed
formation
four
bonds
was
utilization
1,2-boron
shift
rigorous
capitalization
polarities
stabilities.
Thorough
mechanistic
studies
were
carried
out,
synthetic
utility
obtained
products
demonstrated
various
downstream
modifications.
Notably,
addition
functionalization
individual
groups,
their
interplay
gave
rise
unique
array
cyclic
products.
Organic Letters,
Год журнала:
2024,
Номер
26(3), С. 713 - 718
Опубликована: Янв. 12, 2024
Sulfonamides
are
important
structures
in
pharmaceuticals,
agrochemicals,
and
organocatalysts,
yet
the
rapid
benign
synthesis
of
these
compounds
is
still
a
great
challenge.
Herein
we
report
photoinduced
method
for
synthesizing
sulfonamides
from
(hetero)aryl
carboxylic
acid
oxime
esters.
This
reaction
proceeds
via
one-pot
cascade
radical–radical
cross-coupling
by
energy-transfer-mediated
photocatalysis.
A
wide
substrate
scope
including
substrates
late-stage
modification
pharmaceutical
molecular
entities
reveal
its
generality.
