Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(27)
Published: May 8, 2023
Abstract
Transition‐metal
catalyzed
enantioconvergent
cross‐coupling
of
tertiary
alkyl
halides
with
ammonia
offers
a
rapid
avenue
to
chiral
unnatural
α,α‐disubstituted
amino
acids.
However,
the
construction
C−N
bonds
between
tertiary‐carbon
electrophiles
and
nitrogen
nucleophiles
presented
great
challenge
owing
steric
congestion.
We
report
copper‐catalyzed
radical
sulfoximines
(as
surrogates)
under
mild
conditions
by
employing
anionic
N,N,N‐ligand
long
spreading
side
arm.
An
array
acid
derivatives
were
obtained
good
efficiency
enantioselectivity.
The
synthetic
utility
strategy
has
been
showcased
elaboration
coupling
products
into
different
α‐fully
substituted
amine
building
blocks.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(38), P. 17319 - 17329
Published: Sept. 1, 2022
The
enantioconvergent
cross-coupling
of
racemic
alkyl
halides
represents
a
powerful
tool
for
the
synthesis
enantioenriched
molecules.
In
this
regard,
first-row
transition
metal
catalysis
provides
suitable
mechanism
stereoconvergence
by
converting
to
prochiral
radical
intermediates
owing
their
good
single-electron
transfer
ability.
contrast
noble
development
chiral
nickel
catalyst,
copper-catalyzed
is
less
studied.
Besides
enantiocontrol
issue,
major
challenge
arises
from
weak
reducing
capability
copper
that
slows
reaction
initiation.
Recently,
significant
efforts
have
been
dedicated
basic
research
aimed
at
developing
ligands
halides.
This
perspective
will
discuss
advances
in
burgeoning
area
with
particular
emphasis
on
strategic
anionic
ligand
design
tune
initiation
under
thermal
conditions
our
group.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(10), P. 4550 - 4558
Published: March 7, 2022
Transition-metal
catalysis
of
substitution
reactions
alkyl
electrophiles
by
nitrogen
nucleophiles
is
beginning
to
emerge
as
a
powerful
strategy
for
synthesizing
higher-order
amines,
well
controlling
their
stereochemistry.
Herein,
we
report
that
readily
accessible
chiral
copper
catalyst
(commercially
available
components)
can
achieve
the
photoinduced,
enantioconvergent
coupling
variety
racemic
tertiary
with
aniline
generate
new
C–N
bond
good
ee
at
fully
substituted
stereocenter
product;
whereas
this
copper-catalyzed
proceeds
−78
°C,
in
absence
light
and
catalyst,
virtually
no
formation
observed
even
upon
heating
80
°C.
The
mechanism
catalytic
process
has
been
interrogated
aid
wide
array
tools,
including
independent
synthesis
proposed
intermediates
reactivity
studies,
spectroscopic
investigations
featuring
photophysical
EPR
data,
DFT
calculations.
These
studies
led
identification
three
copper-based
cycle,
three-coordinate
formally
copper(II)–anilido
(DFT
analysis
points
its
formulation
copper(I)–anilidyl
radical)
complex
serves
persistent
radical
couples
organic
desired
enantioselectivity.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(8)
Published: Dec. 28, 2022
Herein,
we
describe
the
development
of
a
copper-catalyzed
C(sp3
)-amination
proaromatic
dihydroquinazolinones
derived
from
ketones.
The
reaction
is
enabled
by
intermediacy
open-shell
species
arising
homolytic
C-C
bond-cleavage
driven
aromatization.
protocol
characterized
its
operational
simplicity
and
generality,
including
chemical
diversification
advanced
intermediates.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(45), P. 13611 - 13616
Published: Jan. 1, 2022
Sulfoximines
are
synthetically
important
scaffolds
and
serve
roles
in
drug
discovery.
Currently,
there
is
no
solution
to
decarboxylative
sulfoximination
of
benzoic
acids;
although
thoroughly
investigated,
limited
substrate
scope
harsh
reaction
conditions
still
hold
back
traditional
thermal
aromatic
functionalization.
Herein,
we
realize
the
first
acids
via
photo-induced
ligand
copper
charge
transfer
(copper-LMCT)-enabled
carbometalation.
The
transformation
proceeds
under
mild
conditions,
has
a
broad
scope,
can
be
applied
late-stage
functionalization
complex
small
molecules.
Science,
Journal Year:
2023,
Volume and Issue:
379(6633), P. 662 - 670
Published: Feb. 16, 2023
Despite
the
importance
of
enantioenriched
alcohols
in
medicinal
chemistry,
total
synthesis,
and
materials
science,
efficient
selective
construction
tertiary
bearing
two
contiguous
stereocenters
has
remained
a
substantial
challenge.
We
report
platform
for
their
preparation
through
enantioconvergent,
nickel-catalyzed
addition
organoboronates
to
racemic,
nonactivated
ketones.
prepared
several
important
classes
α,β-chiral
single
step
with
high
levels
diastereo-
enantioselectivity
dynamic
kinetic
asymmetric
aryl
alkenyl
nucleophiles.
applied
this
protocol
modify
profen
drugs
rapidly
synthesize
biologically
relevant
molecules.
expect
nickel-catalyzed,
base-free
ketone
racemization
process
be
widely
applicable
strategy
development
processes.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(20), P. 11817 - 11893
Published: Oct. 4, 2023
Enantioconvergent
catalysis
has
expanded
asymmetric
synthesis
to
new
methodologies
able
convert
racemic
compounds
into
a
single
enantiomer.
This
review
covers
recent
advances
in
transition-metal-catalyzed
transformations,
such
as
radical-based
cross-coupling
of
alkyl
electrophiles
with
nucleophiles
or
alkylmetals
and
reductive
two
mainly
under
Ni/bis(oxazoline)
catalysis.
C–H
functionalization
can
be
performed
an
enantioconvergent
manner.
Hydroalkylation
alkenes,
allenes,
acetylenes
is
alternative
reactions.
Hydrogen
autotransfer
been
applied
amination
alcohols
C–C
bond
forming
reactions
(Guerbet
reaction).
Other
metal-catalyzed
involve
addition
allylic
systems
carbonyl
compounds,
propargylation
phenols,
3-bromooxindoles,
allenylation
allenolates
propargyl
bromides,
hydroxylation
1,3-dicarbonyl
compounds.
