Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(49)
Published: Oct. 12, 2022
Secondary
α,α-dialkyl
boronates
are
widely
used
due
to
their
great
versatility.
Herein
we
report
an
unprecedented
deoxygenative
alkylboration
of
aldehydes,
a
facile
method
access
this
type
products.
A
sequence
difunctionalization
can
be
obtained
smoothly
from
the
readily
available
aldehydes
in
only
two
steps.
This
rather
than
conventional
alkenes
also
opens
new
possibilities
within
field.
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.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(6), P. 4162 - 4184
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
summary
of
recent
advances
in
nickel-catalyzed
reactions
employing
tertiary
alkyl
electrophiles
for
the
construction
quaternary
carbon
centers.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Feb. 26, 2021
Abstract
To
increase
the
reliability
and
success
rate
of
drug
discovery,
efforts
have
been
made
to
C(
sp
3
)
fraction
avoid
flat
molecules.
-Rich
enantiopure
amines
are
most
frequently
encountered
as
chiral
auxiliaries,
synthetic
intermediates
for
pharmaceutical
agents
bioactive
natural
products.
Streamlined
construction
aliphatic
has
long
regarded
a
paramount
challenge.
Mainstream
approaches,
including
hydrogenation
enamines
imines,
C–H
amination,
alkylation
were
applied
synthesis
with
circumscribed
skeleton
structures;
typically,
carbon
centre
was
adjacent
an
auxiliary
aryl
or
ester
group.
Herein,
we
report
mild
general
nickel-catalysed
asymmetric
reductive
hydroalkylation
effectively
convert
enamides
enecarbamates
into
drug-like
α-branched
derivatives.
This
reaction
involves
regio-
stereoselective
hydrometallation
enamide
enecarbamate
generate
catalytic
amount
enantioenriched
alkylnickel
intermediate,
followed
by
C–C
bond
formation
via
alkyl
electrophiles.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(23), P. 12532 - 12540
Published: May 30, 2023
An
asymmetric
three-component
carbosulfonylation
of
alkenes
is
presented
here.
The
reaction,
involving
the
simultaneous
formation
a
C-C
and
C-S
bond
across
π-system,
uses
dual
nickel/photoredox
catalytic
system
to
produce
both
β-aryl
β-alkenyl
sulfones
in
high
yields
with
excellent
levels
stereocontrol
(up
99:1
er).
This
protocol
exhibits
broad
substrate
scope
functional
group
tolerance
its
synthetic
potential
has
been
demonstrated
by
successful
applications
toward
pharmacologically
relevant
molecules.
A
array
control
experiments
supports
involvement
secondary
alkyl
radical
intermediate
generated
through
addition
sulfonyl
double
bond.
Moreover,
stoichiometric
cross-over
further
suggest
an
underlying
Ni(0)/Ni(I)/Ni(III)
pathway
operative
these
transformations.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(13), P. 7405 - 7411
Published: Dec. 10, 2020
Abstract
Catalytic
alkene
difunctionalization
is
a
powerful
strategy
for
the
rapid
assembly
of
complex
molecules
and
has
wide
range
applications
in
synthetic
chemistry.
Despite
significant
progress,
compelling
challenge
that
still
needs
to
be
solved
installation
highly
functionalized
C(sp
3
)‐hybridized
centers
without
requiring
pre‐activated
substrates.
We
herein
report
inexpensive
easy‐to‐synthesize
decatungstate
photo‐HAT,
combination
with
nickel
catalysis,
provides
versatile
platform
three‐component
through
direct
selective
activation
aliphatic
C−H
bonds.
Compared
previous
studies,
advantages
this
are
most
abundant
hydrocarbons
used
as
feedstocks,
various
tertiary,
secondary,
primary
)‐hybrid
can
easily
installed.
The
practicability
demonstrated
late‐stage
functionalization
natural
products
concise
synthesis
pharmaceutically
relevant
including
Piragliatin.
Science,
Journal Year:
2021,
Volume and Issue:
374(6566), P. 432 - 439
Published: Oct. 22, 2021
Iron
links
a
trio
holds
particular
appeal
as
catalytic
metal—it
is
safe
and
abundant,
well
mainstay
of
enzymatic
reactivity.
Nonetheless,
in
synthetic
construction
carbon-carbon
bonds,
modern
chemists
have
largely
had
to
rely
on
rarer
metals
such
palladium.
Liu
et
al
.
now
report
that
coordination
iron
by
bulky
chelating
phosphine
ligand
enables
efficient
mutual
coupling
three
different
reactants—an
alkyl
halide,
an
aryl
Grignard,
olefin—to
form
two
bonds
(see
the
Perspective
Lefèvre).
A
combination
Mössbauer
spectroscopy,
crystallography,
computational
simulations
illuminates
mechanism.
—JSY
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
58(6), P. 730 - 746
Published: Dec. 8, 2021
This
article
provides
a
comprehensive
perspective
on
three-component
1,2-dicarbofunctionalization
of
alkenes
involving
alkyl
radicals,
which
generated
from
structurally
diverse
electrophilic
and
nucleophilic
precursors
under
mild
conditions.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(24), P. 7256 - 7263
Published: Jan. 1, 2022
Various
commercially
available
acyl
chlorides,
aldehydes,
and
alkanes
were
exploited
for
versatile
three-component
1,2-carboacylations
of
alkenes
to
forge
two
vicinal
C-C
bonds
through
the
cooperative
action
nickel
sodium
decatungstate
catalysis.
A
wealth
ketones
with
high
levels
structural
complexity
was
rapidly
obtained
via
direct
functionalization
C(sp2)/C(sp3)-H
in
a
modular
manner.
Furthermore,
regioselective
late-stage
modification
natural
products
showcased
practical
utility
strategy,
generally
featuring
resource
economy
ample
substrate
scope.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(22), P. 3938 - 3943
Published: May 23, 2022
An
electron
donor-acceptor
complex-enabled,
nickel-catalyzed
three-component
net-reductive
1,2-alkylacylation
of
alkenes
is
developed.
This
conjunctive
reductive
acyl
cross-coupling
process
obviates
the
use
an
exogenous
photocatalyst
and
a
stoichiometric
metal-based
reductant,
affording
various
synthetically
useful
1,3-dicarbonyl
compounds
in
good
yields
with
broad
substrate
scope
excellent
functional
group
tolerance.
Both
alkyl
electrophiles
are
derived
from
highly
abundant
readily
accessible
carboxylic
acids,
making
catalytic
1,2-dicarbofunctionalization
more
general
sustainable.
