The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(23), P. 16090 - 16098
Published: Nov. 12, 2022
We
report
herein
a
facile
strategy
to
synthesize
trifluoromethylated
γ-lactams
through
trifluoromethylcarbonylation
of
N-cyano
alkenes
using
readily
available
CF3SO2Na
as
the
CF3
radical
source.
A
range
trifluoromethyl-containing
was
obtained
in
good
yields.
This
transition-metal-free
protocol
is
demonstrated
with
mild
conditions,
broad
substrate
scope,
functional
group
tolerance,
convenient
reagents,
and
an
easy-to-handle
operating
system.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(15), P. 8498 - 8509
Published: April 6, 2023
Nickel
catalysts
of
chiral
pyrox
ligands
promoted
enantioselective
reductive
arylation
and
heteroarylation
aldimines,
using
directly
(hetero)aryl
halides
sulfonates.
The
catalytic
can
also
be
conducted
with
crude
aldimines
generated
from
condensation
aldehydes
azaaryl
amines.
Mechanistically,
density
functional
theory
(DFT)
calculations
experiments
pointed
to
an
elementary
step
1,4-addition
aryl
nickel(I)
complexes
N-azaaryl
aldimines.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 15, 2024
A
single-atom
catalyst
with
generally
regarded
inert
Zn–N4
motifs
derived
from
ZIF-8
is
unexpectedly
efficient
for
the
activation
of
alcohols,
enabling
alcohol-mediated
alkylation
and
transfer
hydrogenation.
C-alkylation
nitriles,
ketones,
N-heterocycles,
amides,
keto
acids,
esters,
N-alkylation
amines
amides
all
go
smoothly
developed
method.
Taking
α-alkylation
nitriles
alcohols
as
an
example,
starts
(1)
nitrogen-doped
carbon
support
catalyzed
dehydrogenation
into
aldehydes,
which
further
condensed
to
give
vinyl
followed
by
(2)
hydrogenation
C=C
bonds
in
on
sites.
The
experimental
results
DFT
calculations
reveal
that
Lewis
acidic
Zn-N4
sites
promote
step
activating
alcohols.
This
first
example
highly
catalysts
various
organic
transformations
biomass-derived
alkylating
reagents
hydrogen
donors.
Using
carbonyl
compounds
or
synthesis
α-alkylated
appealing
a
sustainability
perspective.
Here,
acting
acid
effectively
activates
thus
promoting
reactions
using
both
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(13), P. 9404 - 9412
Published: March 20, 2024
The
catalytic
and
enantioselective
construction
of
quaternary
(all-carbon
substituents)
stereocenters
poses
a
formidable
challenge
in
organic
synthesis
due
to
the
hindrance
caused
by
steric
factors.
One
conceptually
viable
potentially
versatile
approach
is
coupling
C–C
bond
through
an
outer-sphere
mechanism,
accompanied
realization
enantiocontrol
cooperative
catalysis;
however,
examples
such
processes
are
yet
be
identified.
Herein,
we
present
method
for
creating
different
compounds
with
photoredox/Fe/chiral
primary
amine
triple
catalysis.
This
facilitates
connection
unactivated
alkyl
source
tertiary
moiety,
which
also
rare.
scalable
process
exhibits
mild
conditions,
does
not
necessitate
use
base,
possesses
good
functional-group
tolerance.
Preliminary
investigations
into
underlying
mechanisms
have
provided
valuable
insights
reaction
pathway.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(19), P. 12895 - 12900
Published: May 2, 2024
A
nickel
complex
of
chiral
bisoxazolines
catalyzed
the
stereoselective
reductive
arylation
ketones
in
high
enantioselectivity.
range
common
acyclic
and
cyclic
reacted
without
aid
directing
groups.
Mechanistic
studies
using
isolated
a
bis(oxazoline)
(L)Ni(Ar)Br
revealed
that
Mn
reduction
was
not
needed,
while
Lewis
acidic
titanium
alkoxides
were
critical
to
ketone
insertion.
Organic Process Research & Development,
Journal Year:
2023,
Volume and Issue:
27(3), P. 423 - 447
Published: Feb. 17, 2023
Nonprecious-metal-catalyzed
alternatives
to
powerful
precious
metal
transformations
are
of
increasing
interest
in
academia
and
the
pharmaceutical
industry
due
lower
cost,
better
sustainability,
toxicity.
With
continual
growth
broad
field
nonprecious
catalysis
(NPMC),
we
have
chosen
highlight
selected
articles
published
from
March
June
2022
which
intended
examples
NPMC
that
feel
may
be
especially
relevant
development.
We
aim
inspire
academic
industrial
innovation
through
discussion
herein.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(5), P. 2884 - 2900
Published: Jan. 25, 2023
The
involvement
of
planar
carbocation
intermediates
is
generally
considered
undesirable
in
asymmetric
catalysis
due
to
the
difficulty
gaining
facial
control
and
their
intrinsic
stability
issues.
Recently,
suitably
designed
chiral
catalyst(s)
have
enabled
a
guided
approach
nucleophiles
one
prochiral
faces
carbocations
affording
high
enantiocontrol.
Herein,
we
present
vital
mechanistic
insights
from
our
comprehensive
density
functional
theory
(B3LYP-D3)
study
on
Ir-phosphoramidite-catalyzed
reductive
deoxygenation
racemic
tertiary
α-substituted
allenylic
alcohols.
catalytic
transformation
relies
synergistic
action
phosphoramidite-modified
Ir
catalyst
Bi(OTf)3,
first
leading
formation
an
Ir-π-allenyl
intermediate
through
turn-over-determining
SN1
ionization,
followed
by
face-selective
hydride
transfer
Hantzsch
ester
analogue
yield
enantioenriched
product.
Bi(OTf)3
was
found
promote
significant
number
ionic
interactions
as
well
noncovalent
(NCIs)
with
substrates
(allenylic
alcohol
ester),
thus
providing
access
lower
energy
route
compared
pathways
devoid
Bi(OTf)3.
In
nucleophilic
addition,
induction
depend
efficacy
such
key
NCIs.
curious
case
reversal
enantioselectivity,
when
α-substituent
allenyl
changed
methyl
cyclopropyl,
identified
originate
change
mechanism
enantioconvergent
pathway
(α-methyl)
dynamic
kinetic
(α-cyclopropyl).
These
molecular
could
lead
newer
strategies
tame
enantioselective
reactions
using
suitable
combinations
catalysts
additives.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(30), P. 16796 - 16811
Published: July 20, 2023
Synthetic
application
of
asymmetric
catalysis
relies
on
strategic
alignment
bond
construction
to
creation
chirality
a
target
molecule.
Remote
desymmetrization
offers
distinctive
advantages
spatial
decoupling
catalytic
transformation
and
generation
stereogenic
element.
However,
such
separation
presents
substantial
difficulties
for
the
chiral
catalyst
discriminate
distant
enantiotopic
sites
through
reaction
three
or
more
bonds
away
from
prochirality
center.
Here,
we
report
strategy
that
establishes
acyclic
quaternary
carbon
stereocenters
cross-coupling
reactions
at
distal
positions
aryl
substituents.
The
new
class
amino
acid-derived
ionic
catalysts
enables
desymmetrizing
(enantiotopic-group-selective)
Suzuki-Miyaura
reaction,
Sonogashira
Buchwald-Hartwig
amination
between
diverse
diarylmethane
scaffolds
aryl,
alkynyl,
coupling
partners,
providing
rapid
access
enantioenriched
molecules
project
substituents
widely
spaced
in
three-dimensional
space.
Experimental
computational
investigations
reveal
electrostatic
steering
substrates
by
C-terminus
ligands
interactions.
Cooperative
ion-dipole
interactions
catalyst's
amide
group
potassium
cation
aid
preorganization
transmits
asymmetry
product.
This
study
demonstrates
it
is
practical
achieve
precise
long-range
stereocontrol
engineering
arrangements
catalysts'
substrate-recognizing
groups
metal
centers.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 6228 - 6235
Published: April 10, 2024
Chiral
nickel
complexes
promoted
enantioselective
reductive
alkenylation
of
a
range
conjugated
enones,
using
alkenyl
bromides,
triflates,
and
tosylates.
The
neutral
condition
was
compatible
with
sensitive
groups
azaheteroaryl
rings.
Importantly,
in
products
can
be
readily
converted
to
functionalized
alkyl
via
iron-catalyzed
hydrofunctionalization.
Some
examples
asymmetric
N-enoyl
pyrroles
indoles
were
also
included.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(20), P. 13540 - 13560
Published: Oct. 6, 2023
Bidentate
P,N
ligands,
integrating
phosphine
and
nitrogen
donors,
are
highlighted
for
their
versatile
characteristics,
offering
both
electronic
steric
tunability.
Their
hemilabile
nature,
coupled
with
the
ability
to
modulate
properties
through
choice
of
donor
atoms
substituents,
has
expanded
horizons
chemical
transformations.
This
Review
focuses
on
Ni-catalyzed
cross-coupling
reactions
mediated
by
ligands.
The
asymmetrical
nature
each
atom
playing
a
specific
role
in
catalytic
cycle,
offers
control,
stability,
unique
regioselectivity
processes.
In
particular,
Ni/P,N-catalytic
system
exhibits
remarkable
reactivity
π-substrates
including
alkenes,
alkynes,
allenes.
A
thorough
mechanistic
understanding
these
processes
insights
into
trends
future
directions
Ni/P,N-catalyzed
reactions.
