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
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 5735 - 5778
Опубликована: Апрель 1, 2024
The
lack
of
effective
strategies
for
direct
construction
nitrogen–nitrogen
bonds
has
hampered
developments
in
the
synthesis
and
application
molecules
containing
hydrazine
or
azo
motifs.
Attracted
by
their
properties
both
material
science
medicinal
chemistry,
more
attention
been
drawn
to
this
area,
resulting
fast
growth
design
azaheterocycles
substituted
hydrazines.
This
review
focuses
on
efficient
catalytic
approaches
toward
formation
N–N
N═N
through
different
strategies,
including
oxidative
dehydrogenation,
nitrene-transfer
reaction,
reductive
coupling,
some
other
recently
developed
methods.
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 2039 - 2044
Опубликована: Март 4, 2024
We
report
the
synthesis
of
acyl
hydrazides
from
acylsilanes
in
presence
visible
light
without
aid
additives
or
transition
metals.
Acylsilanes
underwent
[1,2]-Brook
rearrangement
to
generate
nucleophilic
siloxycarbenes
which
on
further
addition
N═N
azodicarboxylates
produced
hydrazides.
Control
experiments
indicate
that
reaction
proceeds
through
singlet
carbene
intermediate.
Transformation
hydrazide
functionality
other
functional
groups
was
demonstrated,
including
drug
candidate
Moclobemide.
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14548 - 14555
Опубликована: Янв. 1, 2024
The
fluctuating
reproducibility
of
scientific
reports
presents
a
well-recognised
issue,
frequently
stemming
from
insufficient
standardisation,
transparency
and
lack
information
in
publications.
Green Synthesis and Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 1, 2024
A
highly
selective
and
atom-economical
multi-component
remote
difunctionalization
strategy
has
been
successfully
developed.
This
utilizes
precise
control
over
the
radical
properties
of
bifunctional
precursors
electronic
traits
olefins
diazenes
to
achieve
effective
radical-mediated
1,4-oxyimination/diamination
across
C=C
N=N
bonds.
By
capitalizing
on
compatibility
reactivity
tuning,
this
approach
enables
synthesis
complex
triazine
compounds
with
an
N-N-N
framework,
providing
a
versatile
tool
for
constructing
diverse
molecular
structures.
metal-free
method
is
atom-efficient
adaptable
various
substrates,
demonstrating
remarkable
tolerance
broad
range
functional
groups.
Organic Letters,
Год журнала:
2024,
Номер
26(46), С. 9931 - 9936
Опубликована: Ноя. 11, 2024
In
this
study,
we
have
developed
a
metal-free,
photoinduced
energy
transfer
strategy
for
the
efficient
difunctionalization
of
carbon-nitrogen
double
bonds
(C═N).
Utilizing
oxime
ester-based
bifunctional
reagents,
achieved
direct
radical
C═N
through
nitrogen-nitrogen
coupling,
with
over
35
examples
and
yields
up
to
96%.
This
method
exhibits
broad
substrate
scope,
being
compatible
variety
carboxylic
acids
biologically
active
molecules,
thus
offering
novel
approach
heteroatom-containing
unsaturated
in
synthetic
chemistry.
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 310 - 342
Опубликована: Дек. 17, 2024
The
biological
formation
of
nitrogen–nitrogen
(N–N)
bonds
represents
intriguing
reactions
that
have
attracted
much
attention
in
the
past
decade.
This
interest
has
led
to
an
increasing
number
N–N
bond-containing
natural
products
(NPs)
and
related
enzymes
catalyze
their
(referred
this
review
as
NNzymes)
being
elucidated
studied
greater
detail.
While
more
detailed
information
on
biosynthesis
NPs,
which
only
become
available
recent
years,
provides
unprecedented
source
biosynthetic
enzymes,
potential
for
biocatalytic
applications
been
minimally
explored.
With
review,
we
aim
not
provide
a
comprehensive
overview
both
characterized
NNzymes
hypothetical
biocatalysts
with
putative
bond
forming
activity,
but
also
highlight
from
perspective.
We
present
compare
conventional
synthetic
approaches
linear
cyclic
hydrazines,
hydrazides,
diazo-
nitroso-groups,
triazenes,
triazoles
allow
comparison
enzymatic
routes
via
these
functional
groups.
Moreover,
pathways
well
diversity
reaction
mechanisms
are
presented
according
direct
groups
currently
accessible
enzymes.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 16, 2025
Abstract
Aromatic
compounds
serve
as
key
feedstocks
in
the
chemical
industry,
typically
undergoing
functionalization
or
full
reduction.
However,
partial
reduction
via
dearomative
sequences
remains
underexplored
despite
its
potential
to
rapidly
generate
complex
three-dimensional
scaffolds
and
existing
strategies
often
require
metal-mediated
multistep
processes
suffer
from
limited
applicability.
Herein,
a
photocatalytic
radical
cascade
approach
enabling
difunctionalization
through
selective
spirocyclization/imination
of
nonactivated
arenes
is
reported.
The
method
employs
bifunctional
oxime
esters
carbonates
introduce
multiple
functional
groups
single
step,
forming
spirocyclic
motifs
iminyl
functionalities
N–O
bond
cleavage,
hydrogen-atom
transfer,
addition,
spirocyclization,
radical-radical
cross-coupling.
reaction
constructs
up
four
bonds
(C−O,
C−C,
C−N)
simple
starting
materials.
Its
broad
applicability
demonstrated
on
various
substrates,
including
pharmaceuticals,
it
compatible
with
scale-up
under
flow
conditions,
offering
streamlined
synthesizing
highly
decorated
frameworks.
