Herein,
we
report
an
unprecedented
dual
photoexcited
palladium
and
photoredox-catalyzed
remote
C(sp3)-H
acylation
of
amides
free
external
acylating
reagents
through
sequential
N-O/C-H/C-O
bond
cleavage
chemoselective
C-C
formation.
This
catalytic
system
shows
high
efficiency,
good
atom
economy
by
deletion
oxygen,
diverse
functional
group
tolerance.
Experimental
investigation
the
reaction
mechanism
revealed
that
O-acyl
hydroxamides
enabled
generated
alkyl
radicals
via
a
1,5-HAT
process
mediated
amidyl
carboxylate
complex,
which,
undergoing
phosphoranyl
radical-mediated
C-O
cleavage,
leads
to
coupling
with
deliver
final
products.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(48)
Опубликована: Окт. 11, 2023
Abstract
N
‐Heterocyclic
carbene
(NHC)
catalyzed
radical‐radical
reactions
have
been
proven
to
be
powerful
strategies
for
assembling
ketyl‐containing
compounds
via
single
electron
transfer
(SET)
pathway
under
either
thermal
conditions
or
photoredox
conditions.
In
this
context,
acylation
of
alkenes
radical
relay
NHC‐organocatalysis
has
also
opened
a
new
window
the
difunctionalization
construct
valuable
molecules
in
organic
synthesis.
review,
advances
and
progress
were
summarized
according
different
ways
generation
key
NHC‐bound
ketyl‐type
radicals.
Furthermore,
reaction
scopes,
limitations
mechanisms
discussed
based
on
types
catalytic
systems.
Conclusions
perspectives
put
forward
at
end.
Synthesis,
Год журнала:
2024,
Номер
56(17), С. 2595 - 2613
Опубликована: Янв. 9, 2024
Abstract
Carbonylation
reactions
have
been
widely
used
to
construct
carbonyl-containing
molecules
or
carbon
enhancement
reactions,
which
are
mostly
catalyzed
by
noble
metals
(Pd,
Rh,
Ru,
Ir).
In
this
review,
we
introduce
the
copper-catalyzed
carbonylation
that
developed
in
our
group.
Diverse
using
various
substrates,
including
of
C–H
activated
alkanes,
difunctionalization
unsaturated
C–C
bonds,
and
alkyl
halides
via
radical
pathway.
1
Introduction
2
Cu-Catalyzed
C(sp
3)–H
Bonds
3
Carbonylative
Difunctionalization
Unsaturated
4
Cu–X
(H
B)
Mediated
Acylation
with
Electrophiles
5
6
Alkyl
Halides
7
Other
Types
Copper-Catalyzed
Reactions
8
Conclusion
Outlook
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3089 - 3099
Опубликована: Янв. 1, 2024
NHC
and
photocatalysis
dual-catalyzed
mono/difluoromethylative
acylation
of
1,3-enynes
was
realized,
providing
fluormethyl-substituted
allenyl
ketones.
SO
2
might
play
a
critical
role
in
achieving
high
reactivity
selectivity.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(46), С. 25061 - 25067
Опубликована: Ноя. 8, 2023
A
strategy
to
achieve
photosensitized
[2
+
2]
cycloadditions
by
means
of
temporary
ring
constraint
is
reported.
Specifically,
a
dioxaborole
prepared
that
undergoes
with
wide
variety
alkenes.
This
overcomes
some
challenges
the
cycloaddition
acyclic
substrates.
The
products
can
be
easily
transformed
into
cyclobutyl
diols
or
1,4-dicarbonyl
compounds;
latter
represents
formal
alkene
vicinal
diacylation.
synthetic
utility
this
method
shown
in
synthesis
valuable
heterocycles
and
biatriosporin
D.
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.
Molecules,
Год журнала:
2024,
Номер
29(4), С. 790 - 790
Опубликована: Фев. 8, 2024
Monofluoromethyl
(CH2F)
motifs
exhibit
unique
bioactivities
and
are
considered
privileged
units
in
drug
discovery.
The
radical
monofluoromethylative
difunctionalization
of
alkenes
stands
out
as
an
appealing
approach
to
access
CH2F-containing
compounds.
However,
this
strategy
remains
largely
underdeveloped,
particularly
under
metal-free
conditions.
In
study,
we
report
on
visible
light-mediated
three-component
monofluoromethylation/acylation
styrene
derivatives
employing
NHC
organic
photocatalyst
dual
catalysis.
A
diverse
array
α-aryl-β-monofluoromethyl
ketones
was
successfully
synthesized
with
excellent
functional
group
tolerance
selectivity.
mild
CH2F
generation
from
NaSO2CFH2
holds
potential
for
further
applications
fluoroalkyl
chemistry.
Organic Letters,
Год журнала:
2024,
Номер
26(8), С. 1711 - 1717
Опубликована: Фев. 20, 2024
Herein,
we
report
the
phosphonylacylation
of
alkenes
via
visible-light-induced
N-heterocyclic
carbene
(NHC)
catalysis
to
afford
a
series
γ-ketophosphonates
in
moderate
good
yields.
This
protocol
features
mild
conditions,
free
photocatalyst,
and
compatibility
functional
groups.
The
excited
Breslow
enolate
intermediate
was
proposed
undergo
single-electron
transfer
with
oxime
phosphonate
generate
corresponding
ketyl
radical
phosphonyl
radical.
