Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 5, 2024
Abstract
Herein,
we
introduce
a
novel
method
for
the
synthesis
of
S
‐substituted
isothiourea
compounds
via
selective
1,2‐carboimination
between
oxime
esters
as
bifunctional
reagents
and
C=S
bond
isothiocyanates
under
visible‐light
catalysis.
This
approach
deviates
from
conventional
methods
by
precisely
modulating
substrate
electronics
to
selectively
functionalize
over
C=N
bond,
eliminating
need
strong
bases
high
temperatures
bypassing
formation
thiourea
intermediates.
Consequently,
this
protocol
enables
efficient
one‐step
‐alkyl
isothioureas,
with
featuring
mild
reaction
conditions,
operational
simplicity
broad
scope.
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:
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.
Organic Letters,
Год журнала:
2025,
Номер
27(2), С. 606 - 611
Опубликована: Янв. 6, 2025
Aminophosphonates
serve
as
extremely
important
moieties
with
respect
to
their
activities
in
biological
systems.
However,
incorporating
a
Nitrogen
and
Phosphorus
moiety
by
conventional
techniques
ionic
mode
is
usually
associated
extensive
prefunctionalization
of
the
substrates,
employing
harsh
conditions
reagents
that
limit
viability
these
methods.
Introducing
both
components
radicals
may
be
viable
option.
We
hereby
propose
an
overhaul
existing
reactivity
paradigm
demonstrating
photocatalytic
diradical-based
approach,
where
new
iminophosphonating
are
rationally
designed
developed
used
extensively
homolytic
cleavage
for
simultaneously
installing
iminyl
phosphonyl
groups
onto
alkenes.
Green Chemistry,
Год журнала:
2023,
Номер
25(10), С. 3857 - 3863
Опубликована: Янв. 1, 2023
A
general
and
environmentally
friendly
organic
photo-induced
strategy
was
developed
for
the
synthesis
of
diverse
alkyl-substituted
β-amino
sulfone
derivatives,
including
primary,
secondary,
tertiary
products.
Organic Letters,
Год журнала:
2023,
Номер
25(36), С. 6671 - 6676
Опубликована: Авг. 29, 2023
In
this
study,
a
metal-free
difunctionalization
strategy
for
diazenes
was
developed
using
range
of
bifunctionalization
reagents.
This
involves
unique
N(sp3)–N(sp2)
radical
coupling
between
the
hydrazine
and
imine
radical.
More
than
30
triazane
core
motifs
were
constructed
by
installing
imines
various
functional
groups,
including
alkyl,
phenyl,
cyanoalkyl,
sulfonyl
on
both
ends
nitrogen–nitrogen
bond
in
an
efficient
manner.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(4), С. 1232 - 1250
Опубликована: Дек. 28, 2023
Recent
advances
in
HAT-induced
C(sp
3
)–H
functionalizations
triggered
by
radical
addition
to
alkynes,
including
5-
exo-trig
,
endo-trig
4-
and
6-
cyclization
cascades,
intermolecular
functionalizations,
are
summarized.
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7009 - 7013
Опубликована: Сен. 14, 2023
The
1,2-iminylalkylation
of
diazenes
using
alkyl
iodides
in
combination
with
an
O-benzoyl
oxime
is
reported.
In
this
transformation,
acted
as
a
radical
precursor
and
XAT
mediator.
addition
to
common
iodides,
other
such
iodomethane,
iodomethane-d3,
trifluoroiodomethane,
ethyl
difluoroiodoacetate,
iodoalkanes
containing
unprotected
hydroxyl
amide
groups
can
also
serve
C-radical
precursors
the
electrophilic
acceptors.
