Angewandte Chemie,
Год журнала:
2022,
Номер
135(1)
Опубликована: Сен. 10, 2022
Abstract
We
disclose
herein
an
atroposelective
synthesis
of
novel
bridged
biaryls
containing
medium‐sized
rings
via
N‐heterocyclic
carbene
organocatalysis.
The
reaction
starts
with
addition
the
catalyst
to
aminophenol‐derived
aldimine
substrate.
Subsequent
oxidation
and
intramolecular
desymmetrization
lead
formation
1,3‐oxazepine‐containing
in
good
yields
excellent
enantioselectivities.
These
biaryl
products
can
be
readily
transformed
into
chiral
phosphite
ligands.
Preliminary
density
function
theory
calculations
suggest
that
origin
enantioselectivity
arises
from
more
favorable
frontier
molecular
orbital
interactions
transition
state
leading
major
product.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(15)
Опубликована: Фев. 7, 2023
This
study
establishes
the
first
organocatalytic
enantioselective
synthesis
of
axially
chiral
N,N'-bisindoles
via
phosphoric
acid-catalyzed
formal
(3+2)
cycloadditions
indole-based
enaminones
as
novel
platform
molecules
with
2,3-diketoesters,
where
de
novo
indole-ring
formation
is
involved.
Using
this
new
strategy,
various
were
synthesized
in
good
yields
and
excellent
enantioselectivities
(up
to
87
%
yield
96
ee).
More
importantly,
class
exhibited
some
degree
cytotoxicity
toward
cancer
cells
was
derived
into
phosphine
ligands
high
catalytic
activity.
provides
a
strategy
for
using
asymmetric
organocatalysis
realize
applications
such
scaffolds
medicinal
chemistry
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(14)
Опубликована: Фев. 10, 2023
Axially
chiral
diaryl
ethers
are
a
type
of
unique
atropisomers
bearing
two
potential
axes,
which
have
applications
in
variety
research
fields.
However,
the
catalytic
enantioselective
synthesis
these
ether
is
largely
underexplored
when
compared
to
asymmetric
biaryl
or
other
types
atropisomers.
Herein,
we
report
highly
efficient
through
an
organocatalyzed
desymmetrization
protocol.
The
phosphoric
acid-catalyzed
electrophilic
aromatic
aminations
symmetrical
1,3-benzenediamine
substrates
afforded
series
excellent
yields
and
enantioselectivities.
facile
construction
heterocycles
by
utilizations
1,2-benzenediamine
moiety
products
provided
access
structurally
diverse
novel
azaarene-containing
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(23), С. 12802 - 12811
Опубликована: Июнь 5, 2023
Quinone
methides
are
well-established
intermediates
in
asymmetric
synthesis.
In
contrast,
their
extended
analogues
with
the
carbonyl
and
methide
units
distributed
across
two
different
rings
have
not
been
exploited
Herein,
we
achieved
first
process
involving
such
intermediates.
Specifically,
use
of
suitable
chiral
phosphoric
acids
enabled
situ
generation
2-naphthoquinone
8-methides
corresponding
aza
counterparts
for
mild
one-pot
nucleophilic
addition.
These
processes
provided
rapid
access
to
a
wide
range
previously
less
accessible
remotely
naphthols
naphthylamines
both
high
efficiency
excellent
enantioselectivity.
Control
experiment
DFT
calculations
important
insights
into
reaction
mechanism,
which
likely
involves
acid
molecules
enantiodetermining
transition
states.
This
work
serves
as
proof
concept
exploitation
new
types
quinone
versatile
synthesis,
thus
providing
platform
efficient
construction
remote
benzylic
stereogenic
centers
aromatic
compounds.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(1)
Опубликована: Сен. 10, 2022
Abstract
We
disclose
herein
an
atroposelective
synthesis
of
novel
bridged
biaryls
containing
medium‐sized
rings
via
N‐heterocyclic
carbene
organocatalysis.
The
reaction
starts
with
addition
the
catalyst
to
aminophenol‐derived
aldimine
substrate.
Subsequent
oxidation
and
intramolecular
desymmetrization
lead
formation
1,3‐oxazepine‐containing
in
good
yields
excellent
enantioselectivities.
These
biaryl
products
can
be
readily
transformed
into
chiral
phosphite
ligands.
Preliminary
density
function
theory
calculations
suggest
that
origin
enantioselectivity
arises
from
more
favorable
frontier
molecular
orbital
interactions
transition
state
leading
major
product.
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.
ACS Catalysis,
Год журнала:
2022,
Номер
12(22), С. 13884 - 13896
Опубликована: Окт. 27, 2022
Understanding
the
reaction
mechanisms,
particularly
chiral
induction
mode,
is
critical
for
development
of
new
asymmetric
catalytic
reactions.
Rhodium(III)-catalyzed
C–H
activation
en
route
to
atroposelective
[4
+
2]
annulative
coupling
with
α-diazo
β-ketoesters
has
been
realized,
affording
axially
phenanthrenes
in
good
excellent
enantioselectivity.
A
combination
experimental
and
computational
studies
revealed
a
nontraditional
stereodivergent–convergent
mode.
The
proceeded
rhodafluorene
intermediate,
followed
by
competitive,
constructive,
stereodivergent
migratory
insertions
two
Rh–C(aryl)
bonds
into
carbene
species
give
β-ketoester
intermediates.
Then,
other
bond
migratorily
inserts
ketone
carbonyl
group.
Following
this
stereodetermining
insertion,
an
ester-chelated
rhodium(III)
alkoxide
bearing
poorly
controlled
centers
well-controlled
C(sp2)–C(sp3)
axis
generated.
final
product
delivered
via
stereoconvergent
elimination
retention
axial
chirality
loss
central
chirality.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(21), С. 3630 - 3650
Опубликована: Окт. 3, 2022
Abstract
Electron‐withdrawing
groups
(EWG)
have
emerged
as
a
powerful
tool
for
the
activation
of
various
arenes
to
promote
nucleophilic
dearomative
additions
construction
complicated
chiral
cyclic
structures
under
asymmetric
catalytic
systems.
Nitro‐indoles,
nitro‐benzofurans/benzothiophenes,
and
related
nitro‐heteroarenes
are
widely
applied
in
reaction
with
nucleophiles
construct
enantioenriched
polycyclic
skeletons
via
dearomatization
process.
Meanwhile,
electron‐deficient
azo‐group
nitroso‐group
an
alternative
arenes,
which
enable
formal
aromatic
arylations
electrophilic
aromatics
novel
biaryl
atropisomers.
Besides,
azo‐naphthanenes
served
dipolar
surrogates
dipolarophiles
proceed
cycloadditions
skeletons.
The
EWG‐tethered
arene
has
proven
be
versatile
protocol
structurally
diversified
backbones.
This
review
summarizes
latest
progress
involved
transformations
organo‐
or
transition
metal
catalysis.
magnified
image
Angewandte Chemie,
Год журнала:
2023,
Номер
135(14)
Опубликована: Фев. 10, 2023
Abstract
Axially
chiral
diaryl
ethers
are
a
type
of
unique
atropisomers
bearing
two
potential
axes,
which
have
applications
in
variety
research
fields.
However,
the
catalytic
enantioselective
synthesis
these
ether
is
largely
underexplored
when
compared
to
asymmetric
biaryl
or
other
types
atropisomers.
Herein,
we
report
highly
efficient
through
an
organocatalyzed
desymmetrization
protocol.
The
phosphoric
acid‐catalyzed
electrophilic
aromatic
aminations
symmetrical
1,3‐benzenediamine
substrates
afforded
series
excellent
yields
and
enantioselectivities.
facile
construction
heterocycles
by
utilizations
1,2‐benzenediamine
moiety
products
provided
access
structurally
diverse
novel
azaarene‐containing