Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(22), P. 10173 - 10183
Published: May 7, 2020
Developing
efficient
and
selective
strategies
to
approach
complex
architectures
containing
(multi)stereogenic
centers
has
been
a
long-standing
synthetic
challenge
in
both
academia
industry.
Catalytic
cascade
reactions
represent
powerful
means
of
rapidly
leveraging
molecular
complexity
from
simple
feedstocks.
Unfortunately,
carrying
out
Heck-type
involving
unactivated
(tertiary)
alkyl
halides
remains
an
unmet
owing
unavoidable
β-hydride
elimination.
Herein,
we
show
that
modular,
practical,
general
palladium-catalyzed,
radical
three-component
coupling
can
indeed
overcome
the
aforementioned
limitations
through
interrupted
Heck/allylic
substitution
sequence
mediated
by
visible
light.
Selective
1,4-difunctionalization
1,3-dienes,
such
as
butadiene,
achieved
employing
different
commercially
available
nitrogen-,
oxygen-,
sulfur-,
or
carbon-based
nucleophiles
bromides
(>130
examples,
mostly
>95:5
E/Z,
>20:1
rr).
Sequential
C(sp3)–C(sp3)
C–X
(N,
O,
S)
bonds
have
constructed
efficiently
with
broad
scope
high
functional
group
tolerance.
The
flexibility
versatility
strategy
illustrated
gram-scale
reaction
streamlined
syntheses
ether,
sulfone,
tertiary
amine
products,
some
which
would
be
difficult
access
via
currently
established
methods.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(27), P. 8004 - 8008
Published: May 10, 2017
An
unprecedented
method
that
makes
use
of
the
cooperative
interplay
between
molecular
iodine
and
photoredox
catalysis
has
been
developed
for
dual
light-activated
intramolecular
benzylic
C-H
amination.
Iodine
serves
as
catalyst
formation
a
new
C-N
bond
by
activating
remote
Csp3
-H
(1,5-HAT
process)
under
visible-light
irradiation
while
organic
TPT
effects
reoxidation
catalyst.
To
explain
compatibility
two
involved
photochemical
steps,
key
N-I
activation
was
elucidated
computational
methods.
The
important
implications
combination
non-metallic
main-group
with
photocatalysis.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(19), P. 10871 - 10885
Published: Aug. 28, 2020
Carbon
dioxide
(CO2)
is
an
important
C1
source
for
the
generation
of
carboxylic
acids
and
derivatives.
Stoichiometric
catalytic
carboxylation
nucleophiles,
including
organometallic
reagents,
with
CO2
has
been
widely
investigated.
Since
many
kinds
reagents
are
prepared
from
electrophiles,
transition-metal-catalyzed
direct
diverse
electrophiles
attracted
much
attention
high
step
economy
user-friendly
protocols.
Although
significant
progress
achieved,
use
stoichiometric
metallic
or
pyrophoric
reductants
common.
The
renaissance
photochemistry
seen
numerous
efforts
devoted
to
light-driven
CO2,
which
become
one
most
active
directions
in
this
field.
In
Perspective,
we
summarize
recent
advances
visible-light-driven
reductive
substrates,
such
as
unsaturated
hydrocarbons,
organic
(pseudo)halides,
imines,
presence
mild
electron
donors,
amines,
Hantzsch
esters,
formates.
We
highlight
mechanisms
reactions,
can
proceed
absence
a
photoredox
catalyst
dual
visible
light
photoredox/transition
metal
system.
also
discuss
future
field
offer
some
insight
into
challenges
that
remain.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
57(5), P. 1371 - 1375
Published: Dec. 6, 2017
An
efficient
photoredox/nickel
catalyzed
sulfonylation
reaction
of
aryl,
heteroaryl,
and
vinyl
halides
has
been
achieved
for
the
first
time.
This
newly
developed
protocol
provides
a
versatile
method
synthesis
diverse
aromatic
sulfones
at
room
temperature
shows
excellent
functional
group
tolerance.
The
electrophilic
coupling
partners
are
not
limited
to
bromides
iodides,
but
also
includes
less
reactive
aryl
chlorides
as
suitable
substrates
this
transformation.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(22), P. 10173 - 10183
Published: May 7, 2020
Developing
efficient
and
selective
strategies
to
approach
complex
architectures
containing
(multi)stereogenic
centers
has
been
a
long-standing
synthetic
challenge
in
both
academia
industry.
Catalytic
cascade
reactions
represent
powerful
means
of
rapidly
leveraging
molecular
complexity
from
simple
feedstocks.
Unfortunately,
carrying
out
Heck-type
involving
unactivated
(tertiary)
alkyl
halides
remains
an
unmet
owing
unavoidable
β-hydride
elimination.
Herein,
we
show
that
modular,
practical,
general
palladium-catalyzed,
radical
three-component
coupling
can
indeed
overcome
the
aforementioned
limitations
through
interrupted
Heck/allylic
substitution
sequence
mediated
by
visible
light.
Selective
1,4-difunctionalization
1,3-dienes,
such
as
butadiene,
achieved
employing
different
commercially
available
nitrogen-,
oxygen-,
sulfur-,
or
carbon-based
nucleophiles
bromides
(>130
examples,
mostly
>95:5
E/Z,
>20:1
rr).
Sequential
C(sp3)–C(sp3)
C–X
(N,
O,
S)
bonds
have
constructed
efficiently
with
broad
scope
high
functional
group
tolerance.
The
flexibility
versatility
strategy
illustrated
gram-scale
reaction
streamlined
syntheses
ether,
sulfone,
tertiary
amine
products,
some
which
would
be
difficult
access
via
currently
established
methods.
