The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(19), P. 14205 - 14209
Published: Sept. 22, 2023
Acylsilanes
are
able
to
react
as
nucleophilic
carbene
precursors,
electrophiles,
and
directing
groups
in
C–H
functionalization.
To
date,
some
of
the
products
reportedly
formed
during
transition-metal-catalyzed
photochemical
reactions
involving
acylsilanes
have
been
incorrectly
assigned.
provide
clarity,
we
herein
address
these
structural
misassignments
detail
revised
structures.
New
insights
into
reactivity
were
also
afforded
via
discovery
that
light-induced
siloxy
carbenes
participate
intramolecular
1,2-carbonyl
addition
proximal
esters.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(16), P. 2125 - 2136
Published: Jan. 1, 2024
In
this
feature
article,
we
focus
on
the
photochemical
strategy
for
construction
of
heterocyclic
skeletons,
specifically
highlighting
methods
that
employ
visible
light-promoted
carbene
transfer
reactions.
Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
aims
to
provide
an
overview
of
radical
Brook
rearrangement,
which
is
organized
by
grouping
three
type
reactive
species
generated
via
the
unique
rearrangement
process.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(10), P. 4926 - 4975
Published: Jan. 1, 2024
In
search
for
the
perfect
wave(length).
This
review
is
dedicated
to
recent
efforts
in
development
of
visible
light
driven
photochemical
strategies
occurring
coloured
organic
compounds.
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.
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.
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:
2023,
Volume and Issue:
25(15), P. 2594 - 2599
Published: April 10, 2023
We
herein
demonstrate
the
acylsilane-directed
Rh-catalyzed
arene
C–H
bond
alkylation
with
maleimides.
The
resulting
derivatives
were
utilized
in
visible-light-induced
intramolecular
siloxycarbene-amide
cyclization
for
synthesis
of
new
tricyclic
γ-lactams.
In
parallel,
we
also
harnessed
same
acylsilane
and
maleimide
units
through
[3
+
2]
carbo-annulation
by
using
Ru-catalysis.
A
wide
range
maleimides
aroylsilanes
used
to
establish
broadness
these
transformations.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(6), P. 1282 - 1286
Published: Feb. 1, 2024
Dithioacetals
are
a
frequently
used
motif
in
synthetic
organic
chemistry,
and
most
existing
reports
discuss
only
symmetrical
dithioacetals.
Examples
of
unsymmetrical
dithioacetals
scarce,
few
general
methods
for
the
selective
synthesis
these
compounds
exists.
An
intriguing
visible-light-induced
strategy
has
been
established
this
work
sequential
reactions
S–H
insertion
acetal
exchange
between
acylsilanes
two
different
thiols
that
deliver
wide
variety
moderate
yields.
The
were
obtained
with
high
selectivity,
great
functional
groups
tolerated.
