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.
Science,
Journal Year:
2023,
Volume and Issue:
381(6662), P. 1072 - 1079
Published: Sept. 7, 2023
The
step
that
cleaves
the
carbon-halogen
bond
in
copper-catalyzed
cross-coupling
reactions
remains
ill
defined
because
of
multiple
redox
manifolds
available
to
copper
and
instability
high-valent
product
formed.
We
report
oxidative
addition
α-haloacetonitrile
ionic
neutral
copper(I)
complexes
form
previously
elusive
but
here
fully
characterized
copper(III)
complexes.
stability
these
stems
from
strong
Cu−CF
3
high
barrier
for
C(
CF
)−C(
CH
2
CN
)
bond-forming
reductive
elimination.
mechanistic
studies
we
performed
suggest
proceeds
by
means
two
different
pathways:
an
S
N
2-type
substitution
complex
a
halogen-atom
transfer
complex.
observed
pronounced
ligand
acceleration
addition,
which
correlates
with
couplings
azoles,
amines,
or
alkynes
alkyl
electrophiles.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(17), P. 10925 - 10937
Published: Aug. 22, 2022
Atom
transfer
radical
addition
(ATRA)
reaction
of
alkenes
has
had
a
significant
impact
on
the
field
difunctionalization
alkenes.
Particularly,
in
three-component
photo-ATRA-type
processes,
rich
chemical
space
and
structural
diversity
could
be
achieved
by
smart
combination
redox-active
precursors
third
coupling
components
(e.g.,
halides,
C-,
N-,
O-nucleophiles)
under
mild
conditions.
However,
inherent
complicated
mechanisms
involving
chain
or
outer-sphere
SET
incipient
intermediates
have
led
to
dearth
general
catalytic
methods
for
highly
enantioselective
variants,
especially
those
regarding
asymmetric
intermolecular
C–O
bond
formation.
Here,
we
report
visible-light-induced
copper-catalyzed
with
oxime
esters
carboxylic
acids.
In
this
process,
cross-coupling
between
sp3-hybridized
carbon
radicals
acids
was
enabled
formation
an
aryl
π-bond-engaged
[σ
+
π]-copper
complex.
This
working
hypothesis
renders
naphthyl
extended
conjugation
suitable
substrates
allows
good
stereocontrol.
exhibits
broad
substrate
scope
high
functional
group
tolerance
respect
each
component,
giving
desired
products
generally
yields
enantioselectivity
(>70
examples;
up
97%
ee).
Preliminary
experimental
computational
studies
are
also
performed
gain
insight
into
mechanism
stereoregulatory
elements.
finding
provides
promising
platform
development
other
benzylic-type
radical-based
reactions.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(46), P. 21347 - 21355
Published: Nov. 11, 2022
The
first
copper-catalyzed
enantioselective
[4
+
1]
annulation
of
yne-allylic
esters
with
1,3-dicarbonyl
compounds
was
realized
through
an
elegant
remote
stereocontrol
strategy.
very
ε
regioselective
nucleophilic
substitution
developed
by
employing
a
novel
chiral
copper-vinylvinylidene
species
from
the
new
C4
synthon
esters.
Thus,
greatly
diverse
spirocycles
were
obtained
ample
scope
and
excellent
levels
chemo-,
regio-,
enantioselectivities.
Moreover,
detailed
mechanistic
studies
suggest
Conia-ene
cascade
pathway
on
stereochemical
induction
progress.
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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1635 - 1643
Published: Jan. 5, 2024
Creating
a
perfect
catalyst
to
operate
enzyme-like
chiral
recognition
has
been
long-sought
aim.
A
challenging
example
in
this
context
is
constructing
acyclic
all-carbon
quaternary
stereogenic
centers
by
transition
metal-catalyzed
enantioselective
C–H
activation.
We
now
report
highly
iridium-catalyzed
primary
borylation
of
α-all-carbon
substituted
2,2-dimethyl
amides
enabled
tailor-made
bidentate
boryl
ligand
(CBL).
The
success
the
current
transformation
attributed
CBL/iridium
catalyst,
which
confined
pocket.
This
protocol
provides
diverse
array
stereocenters
with
excellent
enantiocontrol
and
distinct
structural
features.
Computational
study
reveals
that
steric
hindrance
CBL
could
regulate
type
dominant
orbital
interaction
between
substrate,
crucial
conferring
high
induction.
