The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12583 - 12590
Опубликована: Авг. 19, 2024
A
protocol
induced
by
visible
light
for
the
direct
insertion
of
α-carbonyl
carbenes
into
B–H
bond
amine-borane
adducts
has
been
developed
under
conditions
that
are
free
metal
and
photocatalyst.
This
approach
provides
a
straightforward
route
to
various
organoboron
compounds
from
diazo
with
moderate
good
yields.
Mechanistic
investigations
reveal
this
photoinduced
reaction
proceeds
through
concerted
carbene
bond,
generation
α-diazo
esters
may
be
rate-determining
step.
Chemical Reviews,
Год журнала:
2024,
Номер
124(11), С. 7214 - 7261
Опубликована: Май 16, 2024
In
recent
years,
visible
light-induced
reactions
of
diazo
compounds
have
attracted
increasing
attention
in
organic
synthesis,
leading
to
improvement
existing
reactions,
as
well
the
discovery
unprecedented
transformations.
Thus,
photochemical
or
photocatalytic
generation
both
carbenes
and
radicals
provide
milder
tools
toward
these
key
intermediates
for
many
valuable
However,
vast
majority
transformations
represent
new
reactivity
modes
compounds,
which
are
achieved
by
decomposition
photoredox
catalysis.
particular,
use
a
redox-active
photocatalysts
opens
avenue
plethora
radical
reactions.
The
application
methods
led
inaccessible
classical
associated
with
metal
carbenes.
most
cases,
act
sources
but
can
also
serve
acceptors.
Importantly,
described
processes
operate
under
mild,
practical
conditions.
This
Review
describes
this
subfield
compound
chemistry,
particularly
focusing
on
advancements.
Chemical Communications,
Год журнала:
2023,
Номер
59(48), С. 7346 - 7360
Опубликована: Янв. 1, 2023
This
article
discusses
the
photochemistry
of
several
diazo
compounds
undergoing
visible
light-mediated
photolysis
to
generate
free
carbenes
(or
other
highly
reactive
intermediates),
which
can
be
sequentially
trapped
by
different
reacting
partners.
Chemical Communications,
Год журнала:
2024,
Номер
60(16), С. 2125 - 2136
Опубликована: Янв. 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.
Organic Letters,
Год журнала:
2025,
Номер
27(2), С. 709 - 714
Опубликована: Янв. 7, 2025
Herein,
we
present
a
visible-light-induced
protocol
for
the
synthesis
of
highly
functionalized
oxo-bridged
oxocine
skeletons.
This
method
generates
carbenes
via
ortho-acyl
diazo
compounds,
which
are
rapidly
intercepted
by
oxygen
atom
an
intermolecular
acyl
group
to
form
cyclic
1,3-dipole.
The
in
situ
generated
reactive
1,3-dipole
undergoes
facile
formal
[4
+
3]
cycloaddition
with
alkenyl
pyrazolinone,
yielding
[4.2.1]-oxo-bridged
compounds.
Organic Letters,
Год журнала:
2022,
Номер
24(32), С. 6018 - 6023
Опубликована: Авг. 10, 2022
We
disclosed
herein
a
straightforward
photochemical
method
for
the
construction
of
phenanthridines
containing
synthetically
useful
succinate
unit.
The
reaction
occurred
under
visible-light
irradiation
with
cheap
eosin
Y
Na
as
photoredox
catalyst
and
diazo
compound
precursor.
Under
optimal
conditions,
wide
range
were
obtained
in
moderate
to
good
yields.
Note
that
units
final
heterocycles
could
be
easily
transformed
into
many
valuable
structures,
such
γ-butyrolactone,
dihydrofuran-2(3H)-one,
tetrahydrofuran.
Mechanistic
experiments
performed
support
proposed
mechanism.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(44)
Опубликована: Окт. 21, 2022
Abstract
Cyclopropanes
are
one
of
the
most
important
strained
rings
existing
in
various
pharmaceutical
products
and
secondary
metabolites.
They
also
widely
used
total
synthesis
natural
products,
medicinal
chemistry,
materials
science.
In
past
years,
photochemical
cyclopropanation
has
been
gradually
developed
as
a
robust
attractive
synthetic
method
to
prepare
diverse
cyclopropane
backbones.
this
review,
we
summarize
recent
advances
visible
light‐mediated
synthesis,
especially
using
carbene
transfer
strategy
photocatalytic
radical
reactions.
Science,
Год журнала:
2023,
Номер
381(6657), С. 545 - 553
Опубликована: Авг. 3, 2023
Cyclopropanes
are
key
features
in
many
preclinical,
clinical,
and
commercial
drugs,
as
well
natural
products.
The
most
prolific
technique
for
their
synthesis
is
the
metal-catalyzed
reaction
of
an
alkene
with
a
diazoalkane,
highly
energetic
reagent
requiring
stringent
safety
precautions.
Discovery
alternative
innocuous
reagents
remains
ongoing
challenge.
Herein,
we
report
simple
photoredox-catalyzed
intermolecular
cyclopropanation
unactivated
alkenes
active
methylene
compounds.
proceeds
neutral
solvent
under
air
or
dioxygen
(O
2
)
photoredox
catalyst
excited
by
blue
light-emitting
diode
light
iodine
co-catalyst
that
either
added
molecular
generated
situ
from
alkyl
iodides.
Mechanistic
investigations
indicate
photosensitized
O
plays
vital
role
generation
carbon-centered
radicals
both
addition
compounds
to
ring
closure.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 4926 - 4975
Опубликована: Янв. 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,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 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.
Chemical Science,
Год журнала:
2022,
Номер
14(4), С. 843 - 848
Опубликована: Ноя. 29, 2022
While
asymmetric
insertion
of
metal
carbenes
into
H-X
(X
=
C,
N,
O,
etc.)
bonds
has
been
well-established,
control
over
free
is
challenging
due
to
the
presence
strong
background
reactions
and
lack
any
anchor
for
a
catalyst
interaction.
Here
we
have
achieved
first
photo-induced
metal-free
bond
this
type.
With
visible
light
used
as
promoter
chiral
phosphoric
acid
catalyst,
α-diazoesters
aryl
amines
underwent
smooth
N-H
form
enantioenriched
α-aminoesters
with
high
efficiency
good
enantioselectivity
under
mild
conditions.
Key
success
was
use
DMSO
an
additive,
which
served
rapidly
capture
highly
reactive
carbene
intermediate
domesticated
sulfoxonium
ylide.
