Chemical Reviews,
Год журнала:
2023,
Номер
123(20), С. 11817 - 11893
Опубликована: Окт. 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.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(38)
Опубликована: Июль 21, 2022
Abstract
Highly
selective
and
direct
electroreductive
ring‐opening
carboxylation
of
epoxides
with
CO
2
in
an
undivided
cell
is
reported.
This
reaction
shows
broad
substrate
scopes
within
styrene
oxides
under
mild
conditions,
providing
practical
scalable
access
to
important
synthetic
intermediate
β
‐hydroxy
acids.
Mechanistic
studies
show
that
functions
not
only
as
a
carboxylative
reagent
this
but
also
promoter
enable
efficient
chemoselective
transformation
additive‐free
electrochemical
conditions.
Cathodically
generated
α
‐radical
‐carbanion
intermediates
lead
the
regioselective
formation
‐carboxylation
products.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(43), С. 20067 - 20077
Опубликована: Окт. 18, 2022
Aziridines
are
readily
available
C(sp3)
precursors
that
afford
valuable
β-functionalized
amines
upon
ring
opening.
In
this
article,
we
report
a
Ni/photoredox
methodology
for
C(sp3)-C(sp3)
cross-coupling
between
aziridines
and
methyl/1°/2°
aliphatic
alcohols
activated
as
benzaldehyde
dialkyl
acetals.
Orthogonal
activation
modes
of
each
alkyl
coupling
partner
facilitate
cross-selectivity
in
the
bond-forming
reaction:
acetal
is
via
hydrogen
atom
abstraction
β-scission
bromine
radical
(generated
situ
from
single-electron
oxidation
bromide),
whereas
aziridine
at
Ni
center
reduction.
We
demonstrate
an
Ni(II)
azametallacycle,
conventionally
proposed
cross-coupling,
not
intermediate
productive
cross-coupling.
Rather,
stoichiometric
organometallic
linear
free
energy
relationship
studies
indicate
proceeds
Ni(I)
oxidative
addition,
previously
unexplored
elementary
step.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(42), С. 19337 - 19343
Опубликована: Окт. 12, 2022
An
asymmetric
1,2-dicarbofunctionalization
of
unactivated
alkenes
with
aryl
iodides
and
aryl/alkenylboronic
esters
under
nickel/bioxazoline
catalysis
is
disclosed.
A
wide
array
alkenyl
nucleophiles
are
tolerated,
furnishing
the
products
in
good
yield
high
enantioselectivity.
In
addition
to
terminal
alkenes,
1,2-disubstituted
internal
participate
reaction,
establishing
two
contiguous
stereocenters
diastereoselectivity
moderate
combination
experimental
computational
techniques
shed
light
on
mechanism
catalytic
transformation,
pointing
a
closed-shell
pathway
an
enantiodetermining
migratory
insertion
step,
where
stereoinduction
arises
from
synergistic
interactions
between
sterically
bulky
achiral
sulfonamide
directing
group
hemilabile
bidentate
ligand.
Chemical Reviews,
Год журнала:
2023,
Номер
123(20), С. 11817 - 11893
Опубликована: Окт. 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.
