Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(34), P. 13576 - 13604
Published: Jan. 1, 2024
Three-membered
rings,
such
as
epoxides,
aziridines,
oxaziridines,
cyclopropenes,
vinyloxaziridines,
and
azirines,
are
recognized
crucial
pharmacophores
building
blocks
in
organic
chemistry
drug
discovery.
Despite
the
significant
advances
synthesis
of
these
rings
through
photo/electrochemical
methods
over
past
decade,
there
has
currently
been
no
focused
discussion
updated
overviews
on
this
topic.
Therefore,
we
presented
review
article
efficient
three-membered
using
photo-
electrochemical
strategies,
covering
literature
since
2015.
In
study,
a
conceptual
overview
detailed
discussions
were
provided
to
illustrate
advancement
field.
Moreover,
brief
outlines
current
challenges
opportunities
synthesizing
strategies.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 6, 2025
Cyclopropylamines
are
an
important
subclass
of
substituted
cyclopropanes
that
combine
the
unique
electronic
and
steric
properties
with
presence
a
donor
nitrogen
atom.
In
addition
to
their
in
diverse
array
biologically
active
compounds,
cyclopropylamines
utilized
as
synthetic
intermediates,
particularly
ring-opening
or
cycloaddition
reactions.
Consequently,
synthesis
these
compounds
has
constituted
significant
research
topic,
evidenced
by
abundant
published
methods.
widely
used
Curtius
rearrangement,
classical
cyclopropanation
methods
have
been
adapted
integrate
function
(Simmons-Smith
reaction,
metal-catalyzed
reaction
diazo
on
olefins,
Michael-initiated
ring-closure
reactions)
advances
enantioselective
synthesis.
More
recently,
specific
developed
for
preparation
aminocyclopropane
moiety
(Kulinkovich
reactions
applied
amides
nitriles,
cyclopropenes,
involving
C-H
functionalization,
...).
The
topic
this
review
is
present
different
cyclopropylamine
derivatives,
aim
covering
methodological
best
possible,
highlighting
scope,
stereochemical
aspects
future
trends.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: April 6, 2023
Investigations
into
C-H
amidation
reactions
catalysed
by
cationic
half-sandwich
d6
metal
complexes
revealed
that
the
indenyl-derived
catalyst
[Ind*RhCl2
]2
significantly
accelerated
directed
ortho
of
benzoyl
silanes
using
1,4,2-dioxazol-5-ones.
Ring
slippage
involving
a
haptotropic
η5
to
η3
rearrangement
indenyl
complex
proposedly
enables
ligand
substitution
at
centre
proceed
via
associative,
rather
than
dissociative
pathways,
leading
significant
rate
and
yield
enhancements.
Intriguingly,
this
phenomenon
appears
specific
for
weakly
coordinating
carbonyl-based
directing
groups
with
no
acceleration
observed
corresponding
strongly
nitrogen-based
groups.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(10), P. 2039 - 2044
Published: March 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.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(28), P. 5911 - 5916
Published: July 8, 2024
Acylsilanes
are
emerging
bench-stable
reagents
for
the
generation
of
electron-rich
oxycarbenes
that
difficult
to
access
with
unstable
diazo
compounds.
Herein,
we
report
a
siloxycarbene-mediated
stereoselective
synthesis
silyl
enol
ethers
through
visible-light-induced
intermolecular
reactions
between
acylsilanes
and
α,β-unsaturated
ketones.
Both
solvent
low
temperature
important
success
reaction.
This
approach
features
atomic
economics,
exclusive
stereocontrol,
broad
substrate
scope.
The
synthetic
potential
this
methodology
is
demonstrated
by
gram-scale
reaction
various
downstream
transformations
including
requiring
configuration
purity
ethers.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Oct. 16, 2022
Abstract
Developing
photo-induced
cascade
cyclization
of
alkene-tethered
acylsilanes
is
challenging,
because
are
unstable
under
light
irradiation.
Herein,
we
report
that
the
energy
transfer
from
excited
to
a
photocatalyst
possesses
lower
triplet
can
inhibit
undesired
decomposition
acylsilanes.
With
neutral
Eosin
Y
as
photocatalyst,
an
efficient
synthesis
cyclopentanol
derivatives
achieved
with
and
allylic
sulfones.
The
reaction
shows
broad
substrate
scope
synthetic
potential
this
transformation
highlighted
by
construction
which
contain
fused-ring
or
bridged-ring.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(5), P. 1316 - 1321
Published: Jan. 1, 2023
The
last
two
years
have
witnessed
unprecedentedly
wide
applications
of
acylsilanes
in
many
fields
well
beyond
pure
organic
synthesis.
This
highlight
covers
selected
representative
examples
and
focuses
on
their
possible
the
future.
Chemistry - An Asian Journal,
Journal Year:
2024,
Volume and Issue:
19(11)
Published: April 11, 2024
A
mild
protocol
for
hydroacylation
of
enones
through
photosensitization
acyl
silanes
with
thioxanthone
under
blue
light
(455
nm)
irradiation
is
reported.
Brønsted
acid
used
as
a
cocatalyst
in
the
reaction.
The
versatility
method
demonstrated
inter-
and
intramolecular
product
applied
synthesizing
an
anti-HCV
agent.
Mechanistic
insights
are
also
provided
control
experiments.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(11), P. 3250 - 3256
Published: Jan. 1, 2024
An
unusual
visible-light-induced
[1,3]-brook
rearrangement
of
α-ketoacylsilanes
for
cascade
cyclization
with
1,3,5-triazinanes
and
C
,
N
-cyclic
azomethine
imines
has
been
realized
to
assemble
various
β-lactams
pyrazolidinone
scaffolds.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 5796 - 5805
Published: March 25, 2025
The
transition
metal-catalyzed
asymmetric
[n
+
2]
cycloaddition
reaction
with
oxy-substituted
ketene
intermediates
remains
a
synthetic
challenge
due
to
the
limited
availability
of
suitable
precursors.
Herein,
we
report
visible-light-driven,
palladium-catalyzed
[4
vinyl
benzoxazinanones
siloxyketene
intermediates,
generating
structurally
diverse
chiral
quinolinone
derivatives
satisfactory
diastereo-
and
enantioselectivities.
transient
generation
siloxyketenes
from
α-ketoacylsilylanes
through
visible-light-induced
Brook
rearrangement
is
important
for
success
present
cycloaddition.
13C-labeling
experiments
reveal
pathway
involving
[1,3]-silyl
migration
process.
side
arm
effects
BOX
ligand
silyl
steric
hindrance
α-ketoacylsilanes
play
crucial
roles
in
stereoselectivity
control,
theoretical
calculations
provide
insights
into
stereochemical
outcome
reaction.
