Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 23, 2024
There
is
a
pressing
need
for
methods
that
can
connect
enantioenriched
organic
compounds
with
readily
accessible
building
blocks
via
asymmetric
functionalization
of
unreactive
chemical
bonds
in
synthesis
and
medicinal
chemistry.
Herein,
the
chemoselective
cleavage
two
unactivated
C(Ar)-O
same
molecule
disclosed
first
time
through
an
unusual
nickel-catalyzed
carbomagnesiation.
This
reaction
facilitates
evolution
novel
atroposelective
ring-opening
difunctionalization.
Utilizing
available
dibenzo
bicyclic
substrates,
diverse
valuable
axially
chiral
biaryls
are
furnished
high
efficiencies.
Synthetic
elaborations
showcase
application
potential
this
method.
The
features
method
include
good
atom-economy,
multiple
roles
nucleophile,
simple
catalytic
system
enables
precise
magnesiation
α-C(Ar)-O
bond
arylation
β-C(Ar)-O
bond.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Дек. 30, 2024
The
strain-release-driven
reactions
of
bicyclo[1.1.0]butanes
(BCBs)
have
received
significant
attention
from
chemists.
Notably,
1,2-migratory
enabled
by
BCB-derived
B-ate
complexes
effectively
complement
the
initiated
common
BCBs.
desired
products
are
particularly
valuable
for
late-stage
transformations
due
to
presence
C-B
bond.
However,
asymmetric
mediated
boronate
progressed
slowly.
In
this
study,
we
develop
an
synthesis
atropisomers
featuring
cis-cyclobutane
boronic
esters
facilitated
1,2-carbon
or
boron
migration
ring-strained
complexes,
achieving
high
enantioselectivity.
reaction
is
compatible
with
various
aryl,
alkenyl,
alkyl
and
B
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.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(7)
Опубликована: Янв. 2, 2024
Abstract
Chromium‐catalyzed
enantioselective
Nozaki–Hiyama–Kishi
(NHK)
reaction
represents
one
of
the
most
powerful
approaches
for
formation
chiral
carbon‐heteroatom
bond.
However,
construction
sterically
encumbered
tetrasubstituted
stereocenter
through
NHK
still
posts
a
significant
challenge.
Herein,
we
disclose
cobalt‐catalyzed
aza‐NHK
ketimine
with
alkenyl
halide
to
provide
convenient
synthetic
approach
manufacture
enantioenriched
α‐vinylic
amino
acid.
This
protocol
exhibits
excellent
functional
group
tolerance
99
%
ee
in
cases.
Additionally,
this
asymmetric
reductive
method
is
also
applicable
aldimine
access
trisubstituted
stereogenic
centers.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(40), С. 27809 - 27818
Опубликована: Сен. 26, 2024
Larock
isoquinoline
synthesis
is
one
of
the
most
efficient
and
straightforward
approaches
to
construction
3,4-disubstituted
isoquinolines.
However,
there
have
been
no
asymmetric
versions
for
axially
chiral
isoquinolines
since
their
initial
report
in
2001.
Herein,
we
documented
first
example
an
by
employing
Pd(OAc)
Abstract
Phenol
derivatives
are
naturally
abundant
or
can
be
easily
fabricated
from
commercially
accessible
building
blocks.
In
recent
years,
with
the
aim
of
producing
functionally
important
chiral
compounds
in
enantioenriched
form,
there
has
been
initial
progress
development
metal‐catalyzed
cross‐coupling
reactions
that
involve
enantioselective
cleavage
aromatic
C−O
bonds.
This
concept
encompasses
a
review
significant
advancements
this
field,
as
well
associated
strategies.
Moreover,
challenges
and
potential
opportunities
area
also
underscored.
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.
ACS Catalysis,
Год журнала:
2024,
Номер
14(22), С. 17039 - 17045
Опубликована: Ноя. 4, 2024
Herein,
we
demonstrate
the
successful
application
of
reductive
[2
+
4]
annulation
in
atroposelective
de
novo
benzene
ring
formation.
This
nickel-catalyzed
reaction
between
β-substituted
α-naphthylalkynes
and
a
biselectrophile
C(sp2)–X
type
offers
an
efficient
convenient
method
to
prepare
highly
enantioenriched
C1-symmetric
axially
chiral
biaryls
containing
two
preinstalled
functionalities.
The
coupling
products
can
be
used
as
versatile
synthetic
intermediates
access
bidentate
ligands
or
bifunctional
organocatalysts,
their
utility
asymmetric
catalysis
is
also
showcased
this
context.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(27)
Опубликована: Апрель 23, 2024
Abstract
There
is
a
pressing
need
for
methods
that
can
connect
enantioenriched
organic
compounds
with
readily
accessible
building
blocks
via
asymmetric
functionalization
of
unreactive
chemical
bonds
in
synthesis
and
medicinal
chemistry.
Herein,
the
chemoselective
cleavage
two
unactivated
C(Ar)−O
same
molecule
disclosed
first
time
through
an
unusual
nickel‐catalyzed
carbomagnesiation.
This
reaction
facilitates
evolution
novel
atroposelective
ring‐opening
difunctionalization.
Utilizing
available
dibenzo
bicyclic
substrates,
diverse
valuable
axially
chiral
biaryls
are
furnished
high
efficiencies.
Synthetic
elaborations
showcase
application
potential
this
method.
The
features
method
include
good
atom‐economy,
multiple
roles
nucleophile,
simple
catalytic
system
enables
precise
magnesiation
α‐C(Ar)−O
bond
arylation
β‐C(Ar)−O
bond.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 23, 2024
There
is
a
pressing
need
for
methods
that
can
connect
enantioenriched
organic
compounds
with
readily
accessible
building
blocks
via
asymmetric
functionalization
of
unreactive
chemical
bonds
in
synthesis
and
medicinal
chemistry.
Herein,
the
chemoselective
cleavage
two
unactivated
C(Ar)-O
same
molecule
disclosed
first
time
through
an
unusual
nickel-catalyzed
carbomagnesiation.
This
reaction
facilitates
evolution
novel
atroposelective
ring-opening
difunctionalization.
Utilizing
available
dibenzo
bicyclic
substrates,
diverse
valuable
axially
chiral
biaryls
are
furnished
high
efficiencies.
Synthetic
elaborations
showcase
application
potential
this
method.
The
features
method
include
good
atom-economy,
multiple
roles
nucleophile,
simple
catalytic
system
enables
precise
magnesiation
α-C(Ar)-O
bond
arylation
β-C(Ar)-O
bond.
