Angewandte Chemie,
Год журнала:
2022,
Номер
134(43)
Опубликована: Авг. 26, 2022
Abstract
Catalytic
asymmetric
dynamic
kinetic
resolution
of
configurationally
labile
bridged
biaryls
is
emerging
as
a
powerful
strategy
for
atropisomer
synthesis.
However,
the
reported
examples
suffer
from
an
inherent
challenge
reactivity
highly
dependent
on
torsional
strain
biaryl
substrates,
which
significantly
narrows
down
scope
and
hampers
application.
Herein,
we
report
our
discovery
development
strain‐independent
reaction
between
thionolactones
activated
isocyanides.
By
employing
auto‐tandem
silver
catalysis,
universal
synthesis
both
tri
‐
tetra
ortho
‐substituted
thiazole‐containing
was
realized
in
high
yields
with
enantioselectivities.
In
addition,
these
products
could
be
facilely
converted
to
novel
type
bearing
eight‐membered
lactone.
Mechanistic
studies
were
carried
out
elucidate
cause
this
unusual
reactivity.
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.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(43)
Опубликована: Авг. 26, 2022
Catalytic
asymmetric
dynamic
kinetic
resolution
of
configurationally
labile
bridged
biaryls
is
emerging
as
a
powerful
strategy
for
atropisomer
synthesis.
However,
the
reported
examples
suffer
from
an
inherent
challenge
reactivity
highly
dependent
on
torsional
strain
biaryl
substrates,
which
significantly
narrows
down
scope
and
hampers
application.
Herein,
we
report
our
discovery
development
strain-independent
reaction
between
thionolactones
activated
isocyanides.
By
employing
auto-tandem
silver
catalysis,
universal
synthesis
both
tri-
tetra-ortho-substituted
thiazole-containing
was
realized
in
high
yields
with
enantioselectivities.
In
addition,
these
products
could
be
facilely
converted
to
novel
type
bearing
eight-membered
lactone.
Mechanistic
studies
were
carried
out
elucidate
cause
this
unusual
reactivity.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Фев. 26, 2024
Abstract
The
development
of
new
methods
for
regio‐
and
stereoselective
activation
C−O
bonds
in
ethers
holds
significant
promise
synthetic
chemistry,
offering
advantages
terms
environmental
sustainability
economic
efficiency.
Moreover,
the
C−N
atropisomers
represent
a
fascinating
crucial
chiral
system,
extensively
found
natural
products,
pharmaceutical
leads,
frameworks
advanced
materials.
In
this
work,
we
have
introduced
nickel‐catalyzed
enantioselective
carbon‐oxygen
arylation
reaction
atroposelective
synthesis
N
‐arylisoquinoline‐1,3(2
H
,4
)‐diones.
high
regioselectivity
cleavage
benefits
from
stability
situ
formed
(amido)ethenolate
via
oxidative
addition.
Additionally,
self‐activation
aryl
bond
facilitates
under
mild
conditions,
leading
to
outstanding
enantioselectivities.
diverse
post‐functionalizations
axially
isoquinoline‐1,3(2
)‐diones
further
highlighted
utility
protocol
preparing
valuable
atropisomers,
including
phosphine
ligands.
Organic Letters,
Год журнала:
2022,
Номер
24(49), С. 9157 - 9162
Опубликована: Дек. 5, 2022
A
palladium-catalyzed
asymmetric
C-C
bond
activation/carbonylation
of
cyclobutanones
with
CO
has
been
developed.
This
reaction
provided
an
efficient
method
for
the
synthesis
chiral
indanones
bearing
a
quaternary
carbon
stereocenter
in
good
yields
excellent
enantiomeric
ratio,
exhibiting
functional
group
tolerance.
Transformations
products
to
3,4-dihydroquinolin-2(1H)-one
and
1H-indene
further
demonstrated
versatility
this
reaction.
Organic Letters,
Год журнала:
2023,
Номер
25(42), С. 7705 - 7710
Опубликована: Окт. 13, 2023
Chiral
P,N-ligands
are
of
great
interest
and
importance
in
the
fields
metal-catalyzed
enantioselective
transformations
have
found
numerous
applications
spanning
drug
polymer
synthesis.
Here,
modular
assembly
diverse
P-stereogenic
axially
chiral
phosphinooxazoles
ligands
is
achieved
through
palladium-catalyzed
asymmetric
cleavage
C-P
bond/intermolecular
C-H
bond
functionalization
high
atroposelectivities
diastereoselectivities
up
to
>99%
ee
>25:1
dr.
This
protocol
features
broad
substrate
scope
provides
an
avenue
for
facile
construction
new
directly
from
phosphonium
salts
benzoxazoles/benzothiazoles.
Evaluation
synthesized
two
model
catalytic
reactions
illustrates
potential
our
strategy
access
valuable
molecules.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(15), С. 1734 - 1740
Опубликована: Март 30, 2024
Comprehensive
Summary
Axially
chiral
biaryls
represent
the
most
important
class
of
atropisomers,
and
they
widely
exist
in
natural
products
biologically
active
molecules.
They
also
constitute
a
unique
scaffold
for
ligands
catalysts
organic
synthesis.
The
development
synthetic
methods
to
obtain
such
compounds
has
received
widespread
attention,
among
which
catalytically
atroposelective
ring‐opening
configurationally
labile
represents
one
attractive
strategies.
Various
substrates
with
strained
cyclic
structures,
as
renowned
Bringmann's
lactones,
can
undergo
asymmetric
transformation
into
stable
atropisomers.
Known
advancement
primarily
relies
on
metal
catalyst
combined
well‐designed
ligands,
approaches
utilizing
organocatalysis
critical
resolution
strategy
are
notably
scarce.
In
this
study,
we
disclosed
N
‐heterocyclic
carbene
(NHC)‐catalyzed
reaction
biaryl
lactams
via
direct
nucleophilic
activation.
optimized
bulky
ensures
that
proceed
under
mild
conditions,
affording
desired
product
good
excellent
yields
atroposelectivity.
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.
Cell Reports Physical Science,
Год журнала:
2023,
Номер
4(12), С. 101697 - 101697
Опубликована: Ноя. 22, 2023
The
development
of
efficient
processes
for
the
preparation
structurally
diverse
axially
chiral
biaryls
has
been
an
important
goal
in
synthetic
organic
chemistry
and
asymmetric
catalysis.
However,
sharp
contrast
to
well-established
open-chain
biaryls,
catalytic
enantioselective
construction
medium-sized
bridged
remains
underdeveloped.
In
particular,
no
synthesis
such
frameworks
possessing
a
configurationally
stable
stereogenic
C-N
axis
with
step-
or
pot-economy
disclosed.
Herein,
we
report
practical
atropisomeric
eight-membered
lactam-bridged
N-arylindoles
through
conceptually
intriguing
stepwise
cut-and-sew
strategy.
key
success
lies
silver-catalyzed
atroposelective
ring-opening/cyclization
cascade
reaction
N-arylindole
lactams
isocyanoacetates
establish
axial
chirality.
This
method
features
operational
simplicity,
good
functional
group
tolerance,
high
efficiency,
as
well
enantiocontrol.
It
is
also
noteworthy
that
these
scaffolds
exhibit
large
Stokes
shifts,
demonstrating
their
potential
applications
fluorescent
dyes.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(17)
Опубликована: Фев. 22, 2024
Abstract
The
development
of
new
methods
for
regio‐
and
stereoselective
activation
C−O
bonds
in
ethers
holds
significant
promise
synthetic
chemistry,
offering
advantages
terms
environmental
sustainability
economic
efficiency.
Moreover,
the
C−N
atropisomers
represent
a
fascinating
crucial
chiral
system,
extensively
found
natural
products,
pharmaceutical
leads,
frameworks
advanced
materials.
In
this
work,
we
have
introduced
nickel‐catalyzed
enantioselective
carbon‐oxygen
arylation
reaction
atroposelective
synthesis
N
‐arylisoquinoline‐1,3(2
H
,4
)‐diones.
high
regioselectivity
cleavage
benefits
from
stability
situ
formed
(amido)ethenolate
via
oxidative
addition.
Additionally,
self‐activation
aryl
bond
facilitates
under
mild
conditions,
leading
to
outstanding
enantioselectivities.
diverse
post‐functionalizations
axially
isoquinoline‐1,3(2
)‐diones
further
highlighted
utility
protocol
preparing
valuable
atropisomers,
including
phosphine
ligands.
