Accounts of Chemical Research,
Год журнала:
2023,
Номер
56(5), С. 515 - 535
Опубликована: Янв. 23, 2023
ConspectusThe
use
of
quaternary
stereocenters
during
lead
candidate
optimization
continues
to
grow
because
improved
physiochemical
and
pharmacokinetic
profiles
compounds
with
higher
sp3
fraction.
Pd-catalyzed
redox-neutral
alkene
difunctionalization
involving
carbopalladation
alkenes
followed
by
nucleophilic-trapping
σ-alkyl-palladium
intermediates
has
been
developed
as
an
efficient
method
construct
stereocenters.
However,
the
low
chemoselectivity
air
sensitivity
organometallic
nucleophiles,
well
their
availability
accessibility,
limit
scope
application
this
elegant
strategy.
Recently,
Ni-catalyzed
reductive
cross-coupling
evolved
into
a
privileged
strategy
easily
valuable
C(sp3)-C
bonds.
Despite
great
progress,
enantioselective
coupling
C(sp3)
electrophiles
still
relies
on
activated
or
functionalized
alkyl
precursors,
which
are
often
unstable
require
multiple
steps
prepare.
Therefore,
via
selective
cyclization/cross-coupling
was
developed.
This
not
only
offers
robust
practical
alternative
for
traditional
but
also
provides
strategic
complementarity
electrophiles.
In
Account,
we
summarize
latest
results
from
our
laboratory
topic.
These
findings
mainly
include
explorations
in
modulating
enantioselectivity
cyclization
mode
cyclization/cross-couplings.We
will
first
discuss
chiral
heterocycles
focus
effects
ligands,
reductants,
additives
roles
cross-coupling.
A
wide
range
have
explored,
including
aryl
halides,
vinyl
alkynyl
gem-difluoroalkenes,
CO2,
trifluoromethyl
alkenes,
cyano
The
synthetic
potential
approach
demonstrated
synthesis
biologically
active
natural
products
drug
molecules.
Second,
detail
how
tune
steric
nickel
catalysts
modifying
bipyridine
ligands
regiodivergent
cyclization/cross-couplings.
Specifically,
bidentate
favors
exo-selective
cyclization/cross-coupling,
while
carboxylic
acid-modified
ligand
permits
endo-selective
cyclization/cross-coupling.
We
show
activate
amide
substrate
altering
electronic
properties
substituents
nitrogen,
thereby
enabling
nucleophilic
addition
halides
carbonyls.
Further
investigation
led
tunable
cyclization/cross-couplings
(addition
carbonyl
vs
7-endo-cyclization)
divergent
pharmacologically
important
2-benzazepine
frameworks.
Finally,
serendipitously
discover
that
changing
oxidation
state
can
control
migratory
aptitude
different
groups,
thus
providing
switchable
skeletal
rearrangement
transformation
is
high
value
it
represents
conceptually
unprecedented
new
C-C
bond
activation.
Thus,
Account
summarizes
methods
allow
formation
using
variety
insight
relationship
between
structure,
substrate,
selectivity.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(44), С. 23910 - 23917
Опубликована: Окт. 26, 2023
The
merger
of
electrochemistry
and
transition
metal
catalysis
has
emerged
as
a
powerful
tool
to
join
two
electrophiles
in
an
enantioselective
manner.
However,
the
development
electroreductive
cross-couplings
olefins
remains
challenge.
Inspired
by
advantages
synergistic
use
with
nickel
catalysis,
we
present
here
Ni-catalyzed
cross-coupling
acrylates
aryl
halides
alkyl
bromides,
which
affords
chiral
α-aryl
carbonyls
good
excellent
enantioselectivity.
Additionally,
this
catalytic
reaction
can
be
applied
(hetero)aryl
chlorides,
is
difficult
achieve
other
methods.
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
NiI
species
activates
oxidative
addition
bromides
single-electron
transfer.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
ACS Catalysis,
Год журнала:
2022,
Номер
12(15), С. 9779 - 9789
Опубликована: Июль 27, 2022
A
Ni-catalyzed
enantioselective
reductive
three-component
alkylalkenylation
of
β,γ-alkenyl
ketones
with
cis-alkenyl
iodides
and
fluoroalkyl
in
the
presence
Mn
is
reported.
By
leveraging
five-membered
nickellacycles
stabilized
by
pendant
ketone
group
chiral
bis(oxazoline)
(BiOx)
ligand,
this
protocol
allows
efficient
access
to
enantioenriched
β-alkenyl
from
simple
starting
materials.
diverse
electronically
unbiased
alkenes
beyond
that
enables
regioselective
construction
two
C(sp3)–C(sp3)
C(sp3)–(sp2)
bonds
one
single
operation
also
demonstrated.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(26)
Опубликована: Март 14, 2022
The
construction
of
multi-stereocenters
by
a
transition
metal-catalyzed
cross-coupling
reaction
is
major
challenge.
catalytic
desymmetric
functionalization
unactivated
alkenes
remains
largely
unexplored.
Herein,
we
disclose
-a
dicarbofunctionalization
1,6-dienes
via
nickel-catalyzed
reductive
reaction.
leverage
the
underdeveloped
chiral
8-Quinox
enables
Ni-catalyzed
carbamoylalkylation
both
mono-
and
disubstituted
to
form
pyrrolidinone
bearing
two
nonadjacent
stereogenic
centers
in
high
enantio-
stereoselectivitives
with
broad
functional-group
tolerance.
synthetic
application
pyrrolidinones
allows
rapid
access
complex
fused-heterocycles.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(24)
Опубликована: Март 29, 2022
Abstract
A
copper‐catalyzed
asymmetric
aryl
C−P
cross‐coupling/cyclization
reaction
was
successfully
developed
via
dynamic
kinetic
transformation
(DYKAT)
under
mild
conditions.
This
study
provides
a
general
and
simple
method
for
the
catalytic
enantioselective
synthesis
of
stable
six‐,
seven‐
eight‐membered
P‐stereogenic
phosphorus
heterocycles
with
excellent
enantioselectivities
moderate
to
high
yields.
One‐pot
gram‐scale
P‐heterocycle
from
commercially
available
materials
also
accomplished
enantioselectivity
yield.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Сен. 21, 2022
Despite
paramount
applications
of
chiral
trifluoromethylated
compounds
in
medicinal
chemistry
and
materials
science,
limited
strategies
have
been
developed
for
catalytic
asymmetric
synthesis
such
valuable
fluorinated
structures.
Here,
we
report
a
nickel
catalyzed
enantioselective
dicarbofunctionalization
inexpensive
industrial
chemical
3,3,3-trifluoropropene
(TFP)
with
readily
available
tertiary
alkyl
aryl
iodides.
The
reaction
overcomes
the
β-F
elimination
side
TFP,
proceeds
efficiently
under
mild
conditions.
protocol
possesses
advantages,
as
synthetic
convenience,
high
enantioselectivity,
excellent
functional
group
tolerance,
providing
rapid
straightforward
access
to
interest.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(11), С. 4776 - 4782
Опубликована: Март 9, 2022
An
enantioselective
nickel-catalyzed
intramolecular
reductive
cross-coupling
of
C(sp2)
electrophiles
and
cyano
groups
is
reported.
Enantioenriched
CN-containing
all-carbon
quaternary
stereocenters
are
assembled
by
desymmetrizing
cyclization
aryl/alkenyl
halide-tethered
malononitriles.
The
use
an
organic
reductant,
(EtO)2MeSiH,
crucial
to
the
enantioselectivity
reactivity.
Applications
method
demonstrated
through
synthesis
bioactive
molecules
their
cyanated
analogues
total
natural
product
diomuscinone.
This
study
exhibits
potential
coupling
strategies
access
structurally
rigid
synthetically
versatile
from
readily
available
starting
materials.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(30), С. 13461 - 13467
Опубликована: Июль 25, 2022
Asymmetric
cross-electrophile
difunctionalization
of
tethered
alkenes
has
become
a
powerful
tool
for
the
production
chiral
cyclic
scaffolds;
however,
current
studies
all
focus
on
carbocyclization
reactions.
Herein,
we
report
an
N-cyclization-alkylation
reaction
and
thus
showcase
potential
heterocyclization
accessing
new
enantioenriched
architectures.
This
work
establishes
approach
enantioselective
aza-Heck
cyclization/cross-coupling
sequence,
which
remains
long-standing
unsolved
challenge
synthetic
community.
The
proceeds
with
primary,
secondary,
few
tertiary
alkyl
iodides,
use
newly
defined
ligands
gave
highly
pyrrolines
improved
molecular
diversity
under
mild
conditions.
presence
imine
functionality
allows
further
structural
variations.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(24), С. 13008 - 13014
Опубликована: Июнь 7, 2023
Transition-metal-catalyzed
sila-cycloaddition
has
been
a
promising
tool
for
accessing
silacarbocycle
derivatives,
but
the
approach
limited
to
selection
of
well-defined
sila-synthons.
Herein,
we
demonstrate
potential
chlorosilanes,
which
are
industrial
feedstock
chemicals,
this
type
reaction
under
reductive
nickel
catalysis.
This
work
extends
scope
coupling
from
carbocycle
synthesis
and
single
C-Si
bond
formation
reactions.
The
proceeds
mild
conditions
shows
good
substrate
functionality
tolerance,
it
offers
new
access
silacyclopent-3-enes
spiro
silacarbocycles.
optical
properties
several
dithienosiloles
as
well
structural
variations
products
demonstrated.
