Visible-light induced direct C(sp3)–H functionalization: recent advances and future prospects
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5278 - 5305
Published: Jan. 1, 2024
This
review
summarizes
the
latest
methodological
advances
in
photocatalytic
C(sp
3
)–H
functionalization,
with
a
particular
emphasis
on
formation
of
C–P,
C–B,
C–S
bonds,
etc
.,
and
some
prominent
efforts
asymmetric
C–H
functionalization.
Language: Английский
Titanium in photocatalytic organic transformations: current applications and future developments
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(33), P. 6650 - 6664
Published: Jan. 1, 2024
Titanium,
as
an
important
transition
metal,
has
garnered
extensive
attention
in
both
industry
and
academia
due
to
its
excellent
mechanical
properties,
corrosion
resistance,
unique
reactivity
organic
synthesis.
In
the
field
of
photocatalysis,
titanium-based
compounds
such
titanium
dioxide
(TiO
Language: Английский
Photocatalytic Asymmetric Acyl Radical Truce–Smiles Rearrangement for the Synthesis of Enantioenriched α‐Aryl Amides
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(37)
Published: June 18, 2024
The
radical
Truce-Smiles
rearrangement
is
a
straightforward
strategy
for
incorporating
aryl
groups
into
organic
molecules
which
asymmetric
processes
remains
rare.
By
employing
readily
available
and
non-expensive
chiral
auxiliary,
we
developed
highly
efficient
photocatalytic
acyl
alkyl
of
α-substituted
acrylamides
using
tetrabutylammonium
decatungstate
(TBADT)
as
hydrogen
atom-transfer
photocatalyst,
along
with
aldehydes
or
C-H
containing
precursors.
rearranged
products
exhibited
excellent
diastereoselectivities
(7
:
1
to
>98
2
d.r.)
auxiliary
was
easily
removed.
Mechanistic
studies
allowed
understanding
the
transformation
in
density
functional
theory
(DFT)
calculations
provided
insights
stereochemistry-determining
step.
Language: Английский
Photocatalytic Asymmetric Acyl Radical Truce–Smiles Rearrangement for the Synthesis of Enantioenriched α‐Aryl Amides
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(37)
Published: June 18, 2024
Abstract
The
radical
Truce–Smiles
rearrangement
is
a
straightforward
strategy
for
incorporating
aryl
groups
into
organic
molecules
which
asymmetric
processes
remains
rare.
By
employing
readily
available
and
non‐expensive
chiral
auxiliary,
we
developed
highly
efficient
photocatalytic
acyl
alkyl
of
α‐substituted
acrylamides
using
tetrabutylammonium
decatungstate
(TBADT)
as
hydrogen
atom–transfer
photocatalyst,
along
with
aldehydes
or
C−H
containing
precursors.
rearranged
products
exhibited
excellent
diastereoselectivities
(7
:
1
to
>98
2
d.r.)
auxiliary
was
easily
removed.
Mechanistic
studies
allowed
understanding
the
transformation
in
density
functional
theory
(DFT)
calculations
provided
insights
stereochemistry‐determining
step.
Language: Английский
Electroinduced Reductive and Dearomative Alkene-Aldehyde Coupling
Published: June 25, 2024
The
direct
coupling
of
alkene
feedstocks
with
aldehydes
represents
an
expedient
approach
to
the
generation
new
and
structurally
diverse
C(sp3)-hybridized
alcohols
that
are
primed
for
elaborated
into
privileged
architectures.
Despite
their
abundance,
current
disconnection
strategies
enabling
carbon-carbon
π-bonds
remain
challenging
because
contemporary
methods
often
limited
by
substrate
or
functional
group
tolerance,
compatibility
in
complex
molecular
environments.
Here,
we
report
a
between
simple
alkenes,
heteroarenes
unactivated
aliphatic
via
electrochemically
induced
reductive
activation
C–C
π
bonds.
cornerstone
this
is
discovery
rapid
alternating
polarity
(rAP)
electrolysis
access
direct,
highly
reactive
radical
anion
intermediates
derived
from
conjugated
alkenes
heterocyclic
compounds.
Our
developed
catalyst-free
protocol
enables
new,
alcohol
products.
This
achieved
controlled
reduction
C2–C3
π-bond
unprecedented
dearomative
functionalization
Experimental
mechanistic
studies
demonstrate
rAP
necessary
promotes
kinetically
biased
single-electron
over
aldehydes.
Overall,
technology
provides
versatile
olefin
heterocycle
aldehydes,
offering
straightforward
C(sp3)-rich
oxygenated
scaffolds.
Language: Английский
Electroinduced Reductive and Dearomative Alkene-Aldehyde Coupling
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(43), P. 29450 - 29461
Published: Oct. 17, 2024
The
direct
coupling
of
alkene
feedstocks
with
aldehydes
represents
an
expedient
approach
to
the
generation
new
and
structurally
diverse
C(sp3)-hybridized
alcohols
that
are
primed
for
elaboration
into
privileged
architectures.
Despite
their
abundance,
current
disconnection
strategies
enabling
carbon–carbon
π-bonds
remain
challenging
because
contemporary
methods
often
limited
by
substrate
or
functional
group
tolerance
compatibility
in
complex
molecular
environments.
Here,
we
report
a
between
simple
alkenes,
heteroarenes
unactivated
aliphatic
via
electrochemically
induced
reductive
activation
C–C
π-bonds.
cornerstone
this
is
discovery
rapid
alternating
polarity
(rAP)
electrolysis
access
highly
reactive
radical
anion
intermediates
derived
from
conjugated
alkenes
heterocyclic
compounds.
Our
developed
catalyst-free
protocol
enables
alcohol
products.
This
achieved
controlled
reduction
C2–C3
π-bond
unprecedented
dearomative
functionalization
Experimental
mechanistic
studies
demonstrate
kinetically
biased
single-electron
over
aldehydes.
Application
rAP
chemoselective
olefinic
avoids
undesired
saturative
overreduction.
Overall,
technology
provides
versatile
olefin
heterocycle
aldehydes,
offering
straightforward
C(sp3)-rich
oxygenated
scaffolds.
Language: Английский
Two Photocatalytic Pathways for Reductive Dearomatizations of N‐Arylformylindoles by a Visible‐Light Triplet Organocatalyst
Meng‐Yue Ma,
No information about this author
Cai Yiping,
No information about this author
Qin‐Hua Song
No information about this author
et al.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(20), P. 4228 - 4237
Published: Aug. 14, 2024
Abstract
A
visible‐light
triplet
photocatalyst
5‐acetyl‐2‐mercapto‐benzoic
acid
methyl
ester
(AcBSH)
was
developed
through
introducing
acetyl
into
benzenethiolate
to
improve
the
efficiency
of
intersystem
crossing
(ISC)
and
using
o
‐methoxyformyl
increase
molar
extinction
coefficient.
In
photocatalytic
system
AcBSH,
reductive
dearomatization
N
‐arylformylindoles
is
achieved
afford
desired
indolines
in
moderate
excellent
yields,
including
both
indoles
without
(
1
)
with
2‐substituent
2
).
The
a
steric
hindrance
for
conjugation
between
benzoyl
indole
moiety,
makes
exhibit
different
reduction
potentials
E
red
energy
levels
ΔE
T
Thereby,
two
kinds
substrates
undergo
primarily
pathways:
i)
successive
SET/protonation
pathway,
which
merging
photosensitization
via
triplet‐triplet
transfer
(EnT)
photoinduced
SET
,
ii)
single
electron
(SET)
from
concerted
hydrogen
atom
(HAT)
process
.
Language: Английский
Visible‐Light Enabled Synthesis of 1‐Aryl‐3‐Sulfonylmethyl‐1,2,4‐Triazoles by Arylazo Sulfones
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 5, 2024
Abstract
We
present
a
novel
and
highly
efficient
method
for
synthesizing
polyfunctionalized
1,2,4‐triazoles.
This
approach
leverages
visible
light
arylazo
sulfones
in
combination
with
N
‐vinyl
amides,
the
environmentally
friendly
solvent
ethyl
acetate.
Remarkably,
reaction
proceeds
without
need
(photo)catalysts,
ensuring
near‐perfect
atom
economy
producing
only
water
as
by‐product.
exhibits
excellent
functional
group
tolerance
can
be
scaled
both
batch
continuous‐flow
processes.
Language: Английский