Organic Letters,
Год журнала:
2022,
Номер
24(9), С. 1796 - 1801
Опубликована: Март 2, 2022
Here,
we
report
a
nickel-catalyzed
enantioconvergent
hydroalkylation
of
olefins
with
trifluoromethyl-containing
α-alkyl
halides
for
the
synthesis
enantioenriched
trifluoromethylated
alkanes.
This
reaction
employs
readily
available
and
bench-stable
alkenes
as
alkyl
coupling
partners,
featuring
mild
conditions,
broad
substrate
scope,
high
functional
group
tolerance.
The
synthetic
utility
this
method
is
further
demonstrated
in
late-stage
functionalization
range
drug
molecules
natural
products.
Chemical Communications,
Год журнала:
2022,
Номер
58(24), С. 3847 - 3864
Опубликована: Янв. 1, 2022
This
review
summarises
recent
applications
of
pyridinium
salts
in
radical-mediated
difunctionalization
alkenes.
We
hope
this
will
provide
a
comprehensive
overview
topic
and
promote
the
wider
development
application
salts.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(21), С. 11518 - 11523
Опубликована: Май 16, 2023
The
first
examples
of
enantioselective
doubly
decarboxylative
cross
coupling
are
disclosed.
Malonate
half
amides
smoothly
coupled
to
a
variety
primary
carboxylic
acids
after
formation
the
corresponding
redox-active
esters
under
Ni-electrocatalytic
conditions
using
new
chiral
ligand
based
on
PyBox,
resulting
in
with
α-alkylated
stereocenters.
scope
reaction
is
broad,
tolerating
numerous
functional
groups,
and
uniformly
proceeds
high
ee.
Finally,
potential
utility
this
radical–radical
reductive
simplify
synthesis
demonstrated
case
studies.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(18), С. 10411 - 10421
Опубликована: Апрель 26, 2023
Site-
and
enantio-selective
alkyl-alkyl
bond
formation
is
privileged
in
the
retrosynthetic
analysis
due
to
universality
of
sp3-hybridized
carbon
atoms
organic
molecules.
Herein,
we
report
a
nickel-catalyzed
remote
asymmetric
hydroalkylation
alkenyl
ethers
via
synchronous
implementation
alkene
isomerization
enantioselective
C(sp3)-C(sp3)
formation.
Regression
catalyst
structure-activity
relationships
accelerates
rational
ligand
modification
through
modular
regulation.
This
reaction
has
several
advantages
for
synthesizing
chiral
dialkyl
carbinols
their
ether
derivatives,
including
broad
substrate
scope,
good
functional
group
tolerance,
excellent
regioselectivity
(>20:1
regioisomeric
ratio),
high
enantioselectivity
(up
95%
enantiomeric
excess).
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(34)
Опубликована: Июнь 21, 2022
Abstract
Linear,
α‐branched,
and
β‐branched
aliphatic
amines
are
widespread
in
pharmaceuticals,
agrochemicals,
fine
chemicals.
Thus,
the
development
of
direct
efficient
methods
to
these
structures
a
tunable
manner
is
highly
desirable
yet
challenging.
Herein,
catalyst‐controlled
synthesis
linear
from
Ni/Co‐catalyzed
regio‐
site‐selective
hydroalkylations
alkenyl
with
alkyl
halides
developed.
This
catalytic
protocol
features
reliable
prediction
control
coupling
position
alkylation
provide
orthogonal
access
identical
starting
materials.
platform
unlocks
reactivity
selectivity
nickel
hydride
cobalt
chemistry
catalytically
repurpose
three
types
under
mild
conditions.
Accounts of Chemical Research,
Год журнала:
2023,
Номер
56(23), С. 3475 - 3491
Опубликована: Ноя. 16, 2023
ConspectusMigratory
cross-coupling
via
metal
migration
is
a
process
of
significant
academic
and
industrial
interest.
It
provides
an
attractive
alternative
for
the
selective
installation
functional
group
at
remote
C-H
positions
from
simple
precursors,
thus
enabling
direct
synthesis
challenging
structures
not
accessible
with
traditional
cross-coupling.
In
particular,
merger
1,n-Ni/H
shift
nickel,
Ni-catalyzed
migratory
functionalization
precursors
has
undergone
particularly
intense
development
emerged
as
valuable
field
research
in
past
few
years.
This
Account
will
outline
recent
progress
made
this
arena
terms
migration-functionalization
modes,
diverse
functionalizations,
strategies
regio-
stereocontrol.
Mechanistic
studies
synthetic
applications
are
also
discussed.In
detail,
we
systematically
categorize
our
work
into
two
parts
based
on
modes.
first
part,
platform
created
sp3
alkenes
or
alkyl
halides
iterative
1,2-Ni/H
shift-selective
The
key
reactive
Ni(II)H
species
chain-walking
could
be
generated
situ
either
polarity-reversed
fashion
relying
stoichiometric
reductants
(X-Ni(II)-H)
redox-neutral
participation
nucleophilic
coupling
partners
(FG-Ni(II)-H).
One
advantage
associated
NiH
system
use
relatively
stable,
abundant,
safe
olefin
surrogates
instead
sensitive
organometallics
required
reactions.
Another
that
including
carbonation
more
amination
thiolation
smoothly
achieved
suitable
electrophiles
their
precursors.
Finally,
to
address
multifaceted
selectivity
reactivity
issues
asymmetric
reactions,
have
developed
feasible
ligand
relay
catalytic
strategy.
dynamic
exchange
process,
one
promotes
rapid
while
other
highly
stereoselective
coupling.
innovative
strategy
overcomes
formidable
challenge
stemming
difficulty
designing
single
efficiently
promote
both
steps
second
new
sp2
1,4-Ni/H
been
reported.
Starting
readily
available
aryl
vinyl
partners,
situ-generated
aryl-
vinylnickel(II)
undergo
reversible
along
backbone,
subsequent
various
would
allow
access
1,4-migratory
products.
success
was
discovery
appropriate
A
vinyl-to-aryl
successfully
enables
modular
ipso/ortho
difunctionalization
aryl-to-vinyl
functionalized
trisubstituted
alkenes.We
hope
inspire
broad
interest
future
We
strongly
believe
continued
efforts
fascinating
overcome
many
remaining
challenges,
cutting-edge
ligand/catalyst
design
enhance
selectivity,
conceptually
modes
additional
transformations,
in-depth
mechanistic
rational
reaction
design.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(6)
Опубликована: Янв. 8, 2024
Abstract
A
method
for
the
generation
of
tertiary
carbanions
via
a
deaminative
radical‐polar
crossover
is
reported
using
redox
active
imines
from
α‐tertiary
primary
amines.
variety
benzylic
amines
and
amino
esters
can
be
used
in
this
approach,
with
latter
engaging
novel
“aza‐Reformatsky”
reaction.
Electronic
trends
correlate
stability
resulting
carbanion
reaction
efficiency.
The
anions
trapped
different
electrophiles
including
aldehydes,
ketones,
imines,
Michael
acceptors,
H
2
O/D
O.
Selective
anion
formation
achieved
presence
another
equivalent
or
more
acidic
C−H
bond
both
an
inter‐
intramolecular
fashion.
Mechanistic
studies
suggest
intermediacy
discrete
intermediate.
