Angewandte Chemie,
Год журнала:
2022,
Номер
134(52)
Опубликована: Окт. 7, 2022
Abstract
A
direct
strategy
for
the
difunctionalization
of
alkenes,
with
acylation
occurring
at
more
substituted
alkene
position,
would
be
attractive
complex
ketone
synthesis.
We
report
herein
a
reaction
driven
by
single
photocatalyst
that
enables
α‐acylation
in
this
way
introduction
fluoromethyl,
alkyl,
sulfonyl
or
thioether
group
β‐position
high
chemo‐
and
regioselectivity
under
extremely
mild
conditions.
Crucial
to
success
method
are
rate
differences
kinetics
radical
generation
through
single‐electron
transfer
(SET)
between
different
precursors
excited
(PC*).
Thus,
is
first
occupied
derived
from
precursor
can
generated
most
readily,
α‐keto
acids
could
used
as
an
electrophilic
reagent
alkenes.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(39)
Опубликована: Авг. 9, 2022
Here
we
report
an
α-thianthrenium
carbonyl
species,
as
the
equivalent
of
α-carbonyl
carbocation,
which
is
generated
by
radical
conjugate
addition
a
trifluoromethyl
thianthrenium
salt
to
Michael
acceptors.
The
reactivity
allows
for
synthesis
C
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 10, 2025
1,4-Dicarbonyls
are
versatile
synthons
for
the
construction
of
diverse
pharmacophores
and
natural
products.
However,
stereoselective
synthesis
densely
functionalized
1,4-dicarbonyls
is
challenging.
Here,
we
report
a
biocatalytic
route
to
access
chiral
2,3-dihydroxy-1,4-diketones
in
high
yields
up
gram
scale
using
d-fructose-6-phosphate
aldolase
(EcFSA).
The
utility
these
compounds
as
exemplified
enzyme
cascades
with
subsequent
regio-
enzymatic
transamination
form
homochiral
1-pyrrolines
followed
by
chemical
or
reduction
tetrasubstituted
pyrrolidines.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(49)
Опубликована: Окт. 18, 2022
Herein,
we
developed
a
new
procedure
on
1,2-dicarbonylative
cyclization
of
4-aryl-1-butenes
with
alkyl
bromides.
Using
simple
copper
catalyst,
two
molecules
carbon
monoxide
were
introduced
into
the
double
bond
formation
four
C-C
bonds
and
ring.
Various
α-tetralones
2,3-dihydroquinolin-4-ones
formed
in
moderate
to
good
yields.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(52)
Опубликована: Окт. 7, 2022
A
direct
strategy
for
the
difunctionalization
of
alkenes,
with
acylation
occurring
at
more
substituted
alkene
position,
would
be
attractive
complex
ketone
synthesis.
We
report
herein
a
reaction
driven
by
single
photocatalyst
that
enables
α-acylation
in
this
way
introduction
fluoromethyl,
alkyl,
sulfonyl
or
thioether
group
β-position
high
chemo-
and
regioselectivity
under
extremely
mild
conditions.
Crucial
to
success
method
are
rate
differences
kinetics
radical
generation
through
single-electron
transfer
(SET)
between
different
precursors
excited
(PC*).
Thus,
is
first
occupied
derived
from
precursor
can
generated
most
readily,
α-keto
acids
could
used
as
an
electrophilic
reagent
alkenes.
Chemical Communications,
Год журнала:
2022,
Номер
58(98), С. 13624 - 13627
Опубликована: Янв. 1, 2022
The
use
of
the
recently
reported
organic
multi-resonant
thermally
activated
delayed
fluorescence
(MR-TADF)
photocatalyst
DiKTa
allows
for
modular
synthesis
1,4-diketones
under
mild
and
metal-free
conditions.
reaction
proceeds
via
a
three-component
relay
process
in
presence
an
N-heterocyclic
carbene
(NHC)
organocatalyst.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(49)
Опубликована: Июнь 19, 2023
Abstract
1,n‐dicarbonyls
are
one
of
the
most
fascinating
chemical
feedstocks
finding
abundant
usage
in
field
pharmaceuticals.
Besides,
they
utilized
a
plethora
synthesis
general
synthetic
organic
chemistry.
A
number
‘conventional’
methods
available
for
their
synthesis,
such
as
Stetter
reaction,
Baker‐Venkatraman
rearrangement,
oxidation
vicinal
diols,
and
deoxybenzoins,
synonymous
with
unfriendly
reagents
conditions.
In
last
15
years
or
so,
photocatalysis
has
taken
world
chemistry
by
remarkable
renaissance.
It
is
fair
to
say
now
that
everybody
loves
light
photoredox
opened
new
gateway
chemists
towards
milder,
more
simpler
alternatives
previously
methods,
allowing
access
many
sensitive
reactions
products.
this
review,
we
present
readers
photochemical
variety
1,n‐dicarbonyls.
Diverse
photocatalytic
pathways
these
molecules
have
been
discussed,
placing
special
emphasis
on
mechanisms,
giving
reader
an
opportunity
find
all
significant
developments
place.
Molecules,
Год журнала:
2024,
Номер
29(16), С. 3904 - 3904
Опубликована: Авг. 18, 2024
Ketones
are
ubiquitous
patterns
found
in
various
biological
molecules
and
natural
products.
In
recent
years,
a
number
of
acylation
methods
have
been
developed
based
on
the
use
α-oxocarboxylic
acids
as
acyl-transfer
reagents,
with
particular
emphasis
photoinduced
decarboxylative
Abstract
The
present
review
aims
to
provide
an
overview
of
recent
developments
in
photochemical
and
photocatalyzed
synthesis
α‐aryl
carbonyls
via
formation
C(sp)
2
−C(sp)
3
bonds.
approaches
described
are
based
on
the
use
light
as
exclusive
energy
source
for
generation
highly
reactive
carbon
radicals,
cations
or
radical
ions
key
intermediates
process.
Such
strategies
efficiently
compete
with
traditional
routes,
that
require
combined
transition
metal
complexes,
ligands,
additives
often
harsh
reaction
conditions.
Chemical Communications,
Год журнала:
2023,
Номер
59(76), С. 11433 - 11436
Опубликована: Янв. 1, 2023
A
mild
and
inexpensive
approach
to
synthesising
a
series
of
1,4-diketones
in
moderate
excellent
yields
via
1,2-oxo
alkylation
has
been
developed
using
fluorescein
as
photocatalyst
air
an
oxidant.
The
key
features
include
(i)
varied
substrate
scope
(39
examples);
(ii)
good
functional
group
tolerance;
(iii)
unsymmetrical
1,4-dicarbonyls;
(iv)
late-stage
functionalization
thymol
ibuprofen
derivatives;
(v)
the
synthetic
expansion
5-
6-membered
N-,
O-
S-containing
heterocycles.
Angewandte Chemie,
Год журнала:
2022,
Номер
134(49)
Опубликована: Окт. 18, 2022
Abstract
Herein,
we
developed
a
new
procedure
on
1,2‐dicarbonylative
cyclization
of
4‐aryl‐1‐butenes
with
alkyl
bromides.
Using
simple
copper
catalyst,
two
molecules
carbon
monoxide
were
introduced
into
the
double
bond
formation
four
C−C
bonds
and
ring.
Various
α
‐tetralones
2,3‐dihydroquinolin‐4‐ones
formed
in
moderate
to
good
yields.
