Angewandte Chemie,
Год журнала:
2024,
Номер
136(36)
Опубликована: Июнь 15, 2024
Abstract
Axially
chiral
biaryl
δ‐amino
acids
possess
significantly
different
conformational
properties
and
environment
from
centrally
amino
acids,
therefore,
have
drawn
considerable
attention
in
the
fields
of
synthetic
medicinal
chemistry.
Herein,
a
novel
phenanthroline‐potassium
catalyst
has
been
developed
by
constructing
well‐organized
axially
ligand
composed
one
1,10‐phenanthroline
unit
two
1,1′‐bi‐2‐naphthol
(BINOL)
units.
In
presence
this
catalyst,
good
to
excellent
yields
enantioselectivities
(up
99
%
yield,
98
:
2
er)
achieved
ring‐opening
alcoholytic
dynamic
kinetic
resolution
variety
lactams,
thereby
providing
an
efficient
protocol
for
catalytic
asymmetric
synthesis
unnatural
acid
derivatives.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 26, 2024
Abstract
Upgrading
CO
2
to
value‐added
chiral
molecules
via
catalytic
asymmetric
C−C
bond
formation
is
a
highly
important
yet
challenging
task.
Although
great
progress
on
the
of
centrally
carboxylic
acids
has
been
achieved,
construction
axially
with
never
reported
date.
Herein,
we
report
first
synthesis
,
which
enabled
by
nickel‐catalyzed
dynamic
kinetic
reductive
carboxylation
racemic
aza‐biaryl
triflates.
A
variety
acids,
are
valuable
but
difficult
obtain
catalysis,
generated
in
an
enantioconvergent
version.
This
new
methodology
features
good
functional
group
tolerance,
easy
scale‐up,
facile
transformation
and
avoids
cumbersome
steps,
handling
organometallic
reagents
using
stoichiometric
materials.
Mechanistic
investigations
indicate
process
induced
nickel
catalysis.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(49), С. 26747 - 26755
Опубликована: Ноя. 29, 2023
Herein,
we
report
a
cobalt-catalyzed
atroposelective
reductive
cross-coupling
of
racemic
heterobiaryl
tosylates
with
C(sp2)–X
type
electrophile.
Both
aryl
and
alkenyl
halides
are
competent
precursors
for
this
reaction,
providing
variety
heterobiaryls
as
the
products
in
highly
enantioselective
manner
high
functionality
tolerance.
The
related
asymmetric
arylation
alkenylation
discovered
to
proceed
divergent
mechanisms.
reaction
pathway
changes
from
kinetic
resolution
(KR)
when
bromides
iodides
bearing
strong
electron-withdrawing
substitution
on
para-position
employed
starting
materials
an
enantioconvergent
transformation
via
dynamic
KR
configurationally
labile
cobaltacycles
relatively
electron-rich
used.
change
mechanisms
turns
out
arise
relative
rates
two
competing
elementary
steps,
which
epimerization
cyclic
Co(I)
intermediates
their
trapping
by
coupling
electrophiles
C(sp2)-type
oxidative
addition.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 15, 2024
Axially
chiral
biaryl
δ-amino
acids
possess
significantly
different
conformational
properties
and
environment
from
centrally
amino
acids,
therefore,
have
drawn
considerable
attention
in
the
fields
of
synthetic
medicinal
chemistry.
Herein,
a
novel
phenanthroline-potassium
catalyst
has
been
developed
by
constructing
well-organized
axially
ligand
composed
one
1,10-phenanthroline
unit
two
1,1'-bi-2-naphthol
(BINOL)
units.
In
presence
this
catalyst,
good
to
excellent
yields
enantioselectivities
(up
99
%
yield,
98
:
2
er)
achieved
ring-opening
alcoholytic
dynamic
kinetic
resolution
variety
lactams,
thereby
providing
an
efficient
protocol
for
catalytic
asymmetric
synthesis
unnatural
acid
derivatives.
In
this
context,
we
report
a
nickel-catalyzed
dynamic
kinetic
asymmetric
reductive
arylation
of
aldehydes
with
racemic
heterobiaryl
triflates,
offering
series
axially
chiral
heterobiaryls
bearing
centrally
secondary
alcohol
moiety
in
highly
diastereo-
and
enantioselective
manner.
The
simultaneous
control
both
axial
central
stereogenic
elements
the
products
lies
stereoselective
nucleophilic
addition
configurationally
labile
hetereobiaryl
nickel
complex
to
formyl
group
aldehydes.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 23, 2024
Atropisomeric
biaryls
bearing
carbonyl
groups
have
attracted
increasing
attention
due
to
their
prevalence
in
diverse
bioactive
molecules
and
crucial
role
as
efficient
organo-catalysts
or
ligands
asymmetric
transformations.
However,
preparation
often
involves
tedious
multiple
steps,
the
direct
synthesis
via
carbonylation
has
scarcely
been
investigated.
Herein,
we
report
an
palladium-catalyzed
enantioconvergent
aminocarbonylation
of
racemic
heterobiaryl
triflates
with
amines
dynamic
kinetic
transformation
(DyKAT).
This
protocol
features
a
broad
substrate
scope
excellent
compatibility
for
rapid
construction
axially
chiral
amides
good
high
yields
enantioselectivities.
Detailed
mechanistic
investigations
discover
that
base
can
impede
intramolecular
hydrogen
bond-assisted
axis
rotation
products,
thus
allowing
success
achieve
enantioselectivity.
Moreover,
achieved
be
directly
utilized
N,N,N-pincer
copper-catalyzed
enantioselective
formation
C(sp3)-N
C(sp3)-P
bonds.
Axially
containing
not
only
exist
various
drug
candidates
but
also
serve
authors
transformation.
ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8176 - 8183
Опубликована: Май 10, 2024
Axially
chiral
bridged
biaryls
represent
an
important
subset
of
axially
biaryl
scaffolds
in
fields
ranging
from
organic
synthesis
to
biochemistry
materials
science.
While
numerous
catalytic
strategies
have
been
elucidated
for
the
construction
axial
chirality,
enantioenriched
form
remains
underdeveloped.
Herein,
we
demonstrate
approach
synthesize
diverse
through
nickel-catalyzed
kinetic
asymmetric
cleavage
unactivated
aromatic
C–O
bond.
The
system
features
mild
reaction
conditions,
high
resolution
efficiency,
and
versatile
post-functionalizations.
Mechanistic
studies
reveal
impact
nickel
catalyst's
chirality
on
stereochemical
output
this
transformation.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(22)
Опубликована: Март 26, 2024
Abstract
Upgrading
CO
2
to
value‐added
chiral
molecules
via
catalytic
asymmetric
C−C
bond
formation
is
a
highly
important
yet
challenging
task.
Although
great
progress
on
the
of
centrally
carboxylic
acids
has
been
achieved,
construction
axially
with
never
reported
date.
Herein,
we
report
first
synthesis
,
which
enabled
by
nickel‐catalyzed
dynamic
kinetic
reductive
carboxylation
racemic
aza‐biaryl
triflates.
A
variety
acids,
are
valuable
but
difficult
obtain
catalysis,
generated
in
an
enantioconvergent
version.
This
new
methodology
features
good
functional
group
tolerance,
easy
scale‐up,
facile
transformation
and
avoids
cumbersome
steps,
handling
organometallic
reagents
using
stoichiometric
materials.
Mechanistic
investigations
indicate
process
induced
nickel
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 21, 2024
A
symmetric
anion
mediated
dynamic
kinetic
asymmetric
Knoevenagel
reaction
was
established
as
a
general
and
efficient
method
for
accessing
both
N-C
N-N
atropisomers.
The
resulting
highly
enantio-pure
pyridine-2,6(1H,3H)-diones
exhibit
diverse
structures
functional
groups.
key
to
excellent
regio-
remote
enantiocontrol
could
be
owed
the
hydrogen
bond
between
enolate
triflamide
block
of
organocatalyst.
This
connected
iminium
cation
by
chiral
backbone.
mechanism
investigation
via
control
experiments,
correlation
analysis,
density
theory
calculations
further
revealed
how
stereochemical
information
transferred
from
catalyst
into
axially
pyridine-2,6(1H,3H)-diones.
synthetic
applications
also
demonstrated
reaction's
potential.
