Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: March 12, 2021
Abstract
The
flourishing
Ni/photoredox-catalyzed
asymmetric
couplings
typically
rely
on
redox-neutral
reactions.
In
this
work,
we
report
a
reductive
cross-coupling
of
aryl
iodides
and
α-chloroboranes
under
dual
catalytic
regime
to
further
enrich
the
metallaphotoredox
chemistry.
This
approach
proceeds
mild
conditions
(visible
light,
ambient
temperature,
no
strong
base)
access
versatile
benzylic
boronic
esters
with
good
functional
group
tolerance
excellent
enantioselectivities.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1485 - 1542
Published: Nov. 18, 2021
The
merger
of
photoredox
catalysis
with
transition
metal
catalysis,
termed
metallaphotoredox
has
become
a
mainstay
in
synthetic
methodology
over
the
past
decade.
Metallaphotoredox
combined
unparalleled
capacity
for
bond
formation
broad
utility
photoinduced
electron-
and
energy-transfer
processes.
Photocatalytic
substrate
activation
allowed
engagement
simple
starting
materials
metal-mediated
bond-forming
Moreover,
electron
or
energy
transfer
directly
key
organometallic
intermediates
provided
novel
modes
entirely
complementary
to
traditional
catalytic
platforms.
This
Review
details
contextualizes
advancements
molecule
construction
brought
forth
by
metallaphotocatalysis.
Chemical Science,
Journal Year:
2020,
Volume and Issue:
11(17), P. 4287 - 4296
Published: Jan. 1, 2020
Nickel-catalyzed
three-component
alkene
difunctionalization
has
rapidly
emerged
as
a
powerful
tool
for
forging
two
C-C
bonds
in
single
reaction.
Building
upon
the
modes
of
bond
construction
traditional
two-component
cross-coupling,
various
research
groups
have
demonstrated
versatility
nickel
enabling
catalytic
1,2-dicarbofunctionalization
using
wide
range
carbon-based
electrophiles
and
nucleophiles
fully
intermolecular
fashion.
Though
this
area
only
recently,
last
few
years
witnessed
proliferation
publications
on
topic,
underscoring
potential
strategy
to
develop
into
general
platform
that
offers
high
regio-
stereoselectivity.
This
minireview
highlights
recent
progress
alkenes
via
catalysis
discusses
lingering
challenges
within
reactivity
paradigm.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(15), P. 8542 - 8556
Published: July 2, 2020
1,2-Dicarbofunctionalization
of
alkenes
has
emerged
as
an
efficient
synthetic
strategy
for
preparing
substituted
molecules
by
coupling
readily
available
with
electrophiles
and/or
nucleophiles.
Nickel
complexes
serve
effective
catalysts
owing
to
their
tendency
undergo
facile
oxidative
addition
and
slow
β-hydride
elimination,
capability
access
both
two-electron
radical
pathways.
Two-component
alkene
functionalization
reactions
have
achieved
high
chemo-,
regio-,
stereoselectivities
tethering
one
the
partners
substrate.
Three-component
reactions,
however,
often
incorporate
directing
groups
control
selectivity.
Only
a
few
examples
directing-group-free
difunctionalizations
unactivated
been
reported.
Therefore,
great
opportunities
exist
development
three-component
difunctionalization
broad
substrate
scopes
tunable
stereoselectivities.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(13), P. 7587 - 7680
Published: Jan. 1, 2021
Organic
compounds
that
show
Thermally
Activated
Delayed
Fluorescence
(TADF)
have
become
wildly
popular
as
next
generation
emitters
in
organic
light-emitting
diodes
(OLEDs),
but
since
2016,
received
significant
and
increasing
attention
photocatalysts.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(19), P. 10836 - 10856
Published: Jan. 1, 2021
The
catalytic
dicarbofunctionalization
of
unsaturated
π
bonds
represents
a
powerful
platform
for
the
rapid
construction
complex
motifs.
Despite
remarkable
progress,
novel
and
efficient
methods
achieving
such
transformations
under
milder
conditions
with
chemo-,
regio-,
stereoselectivity
still
remain
significant
challenge;
thus,
their
development
is
highly
desirable.
Recently,
merging
nickel
catalysis
radical
chemistry
offers
new
benign
unprecedented
reactivity
selectivity.
In
this
review,
we
summarize
recent
advances
in
area
by
underpinning
domino
involving
capture
to
provide
clear
overview
reaction
designs
mechanistic
scenarios.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(31), P. 13515 - 13522
Published: June 29, 2020
Alkene
dicarbofunctionalizations
enable
the
streamlined
construction
of
aliphatic
structures
and
have
thus
been
subject
intense
research
efforts.
Despite
significant
progress,
catalytic
asymmetric
variants
remain
scarce.
Inspired
by
advantages
reductive
cross-coupling
approaches,
we
present
here
a
highly
efficient
intermolecular
Ni-catalyzed
dicarbofunctionalization
alkenes.
Two
distinct
readily
available
electrophiles,
namely,
Csp2-
Csp3-halides,
are
added
simultaneously
across
variety
olefins
(vinyl
amides,
vinyl
boranes,
phosphonates)
at
room
temperature
in
regio-
enantioselective
manner.
The
reaction,
devoid
sensitive
organometallic
reagents,
takes
advantage
an
situ
generated
chiral
alkyl
Ni(III)-intermediate
to
ensure
stereodefined
outcome
Csp3–Csp2
bond-forming
reaction.
An
(l)-(+)-isoleucine
bisoxazoline
ligand
presence
coordinating
sites
on
alkene
key
for
successful
these
"asymmetric
radical
relayed
couplings"
(ARRRCs).
Further,
multiple
transformations
amides
obtained
this
process
showcase
potential
new
methodology
straightforward
assembly
building
blocks
such
as
primary
secondary
amines
oxazolines,
highlighting
its
synthetic
utility.
Accounts of Chemical Research,
Journal Year:
2021,
Volume and Issue:
54(17), P. 3415 - 3437
Published: Aug. 12, 2021
ConspectusRecently,
alkene
dicarbofunctionalization,
i.e.,
the
powerful
organic
synthesis
method
of
difunctionalization
with
two
carbon
sources,
emerged
as
a
formidable
reaction
immense
promise
to
synthesize
complex
molecules
expeditiously
from
simple
chemicals.
This
is
generally
achieved
transition
metals
(TMs)
through
interception
by
sources
an
alkylmetal
[β-H–C(sp3)–[M]]
species,
key
intermediate
prone
undergo
rapid
β-H
elimination.
Related
prior
reports,
since
Paolo
Chiusoli
and
Catellani's
work
in
1982
[
Tetrahedron
Lett.
1982,
23,
4517],
have
used
bicyclic
disubstituted
terminal
alkenes,
wherein
elimination
avoided
geometric
restriction
or
complete
lack
β-H's.
With
reasoning
that
β-H–C(sp3)–[M]
intermediates
could
be
rendered
amenable
use
first
row
late
TMs
formation
coordination-assisted
transient
metallacycles,
these
strategies
were
implemented
address
problem
dicarbofunctionalization
reactions.Because
catalyze
C(sp3)–C(sp3)
coupling,
Cu
Ni
anticipated
impart
sufficient
stability
intermediates,
generated
catalytically
upon
carbometalation,
for
their
subsequent
electrophiles/nucleophiles
three-component
reactions.
Additionally,
such
innate
property
enable
coupling
partners
entropically
driven
cyclization/coupling
The
cyclometalation
concept
stabilize
intractable
was
hypothesized
when
reactions
performed.
idea
curtail
founded
Whitesides's
J.
Am.
Chem.
Soc.
1976,
98,
6521]
observation
metallacycles
much
slower
than
acyclic
alkylmetals.In
this
Account,
examples
demonstrate
catalysts
alkenylzinc
reagents,
alkyl
halides,
aryl
halides
afford
carbo-
heterocycles.
In
addition,
forming
nickellacycles
enabled
regioselective
performance
various
alkenyl
compounds.
situ
[M]-H
alkenes
after
induced
unprecedented
metallacycle
contraction
process,
which
six-membered
metal-containing
rings
shrank
five-membered
cycles,
allowing
creation
new
carbon–carbon
bonds
at
allylic
(1,3)
positions.
Applications
are
discussed.
Chinese Journal of Chemistry,
Journal Year:
2020,
Volume and Issue:
38(11), P. 1371 - 1394
Published: June 16, 2020
As
a
straightforward
strategy
for
rapidly
increasing
molecular
complexity,
dicarbofunctionalization
of
alkenes
has
attracted
substantial
interests
organic
synthesis,
medicine
chemistry,
and
materials
science.
Nickel‐catalyzed
cascade
dicarbofunctionalizations
have
been
flourished
in
this
area
recently,
nickel‐mediated
radical
pathways
particularly
offer
new
opportunities
conjunctive
cross‐couplings
with
alkyl
coupling
partners.
Herein,
we
give
comprehensive
review
nickel‐catalyzed
through
historical
perspective,
including
intermolecular
three‐component
reactions
intramolecular
reactions.
Among
the
discussed
review,
carbometallation/cross‐coupling
process
addition/cross‐coupling
are
two
major
alkenes.
The
oxidative
cyclization
1,2‐metallate
shift
processes
also
selectively
discussed.
These
methods
overcome
limitations
associated
using
noble
metals
field,
providing
an
efficient
access
to
structurally
diversified
molecules.