Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(47)
Опубликована: Окт. 16, 2023
Abstract
The
direct
C−H
functionalization
of
1,2‐benzazaborines,
especially
asymmetric
version,
remains
a
great
challenge.
Here
we
report
palladium‐catalyzed
enantioselective
olefination
and
allylation
reactions
1,2‐benzazaborines.
This
approach
is
kinetic
resolution
(KR),
providing
various
C−B
axially
chiral
2‐aryl‐1,2‐benzazaborines
3‐substituted
in
generally
high
yields
with
excellent
enantioselectivities
(selectivity
(S)
factor
up
to
354).
synthetic
potential
this
reaction
showcased
by
late‐stage
modification
complex
molecules,
scale‐up
reaction,
applications.
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
Chemical Reviews,
Год журнала:
2024,
Номер
124(14), С. 8657 - 8739
Опубликована: Июль 2, 2024
Chiral
phosphorus
ligands
play
a
crucial
role
in
asymmetric
catalysis
for
the
efficient
synthesis
of
useful
optically
active
compounds.
They
are
largely
categorized
into
two
classes:
backbone
chirality
and
P-stereogenic
ligands.
Most
reported
belong
to
former
class.
Privileged
ones
such
as
BINAP
DuPhos
frequently
employed
wide
range
catalytic
transformations.
In
contrast,
latter
class
has
remained
small
family
many
years
mainly
because
their
synthetic
difficulty.
The
late
1990s
saw
emergence
novel
with
superior
enantioinduction
ability
Rh-catalyzed
hydrogenation
reactions.
Since
then,
numerous
have
been
synthesized
used
This
Review
summarizes
thus
far,
including
stereochemical
electronic
properties
that
afford
high
excellent
enantioselectivities.
Examples
reactions
use
this
described
together
applications
construction
key
intermediates
natural
products
therapeutic
agents.
literature
covered
dates
back
1968
up
until
December
2023,
centering
on
studies
published
later
years.
Chemical Science,
Год журнала:
2021,
Номер
13(1), С. 141 - 148
Опубликована: Ноя. 24, 2021
A
highly
efficient
atroposelective
N
-acylation
reaction
of
quinazolinone
type
benzamides
with
cinnamic
anhydrides
for
the
direct
catalytic
synthesis
optically
active
atropisomeric
derivatives
was
developed.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(33), С. 13124 - 13134
Опубликована: Авг. 12, 2021
Enantioenriched
1,1-silylboryl
alkanes
possess
silyl
and
boryl
groups
that
are
both
connected
to
the
same
stereogenic
carbon
center
at
well-defined
orientations.
As
these
chiral
multifunctionalized
compounds
potentially
offer
two
synthetic
handles,
they
highly
valued
building
blocks
in
asymmetric
synthesis
as
well
medicinal
chemistry.
Despite
potential
usefulness,
efficient
approaches
for
their
preparation
scarce.
Seeking
address
this
deficiency,
an
enantioselective
cobalt-catalyzed
hydrosilylation/hydroboration
cascade
of
terminal
alkynes
has
been
realized.
This
protocol
constitutes
impressive
case
chemo-,
regio-,
stereoselectivity
wherein
different
hydrofunctionalization
events
exquisitely
controlled
by
a
single
set
metal
catalyst
ligand,
operation
which
would
usually
require
separate
catalytic
systems.
Downstream
transformations
enantioenriched
1,1-silyboryl
led
various
valuable
compounds.
Mechanistic
studies
suggest
present
reaction
undergoes
regioselective
stereocontrolled
sequential
hydrosilylation
hydroboration
processes.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(7)
Опубликована: Дек. 20, 2022
Diaryl
ethers
are
widespread
in
biologically
active
compounds,
ligands
and
catalysts.
It
is
known
that
the
diaryl
ether
skeleton
may
exhibit
atropisomerism
when
both
aryl
rings
unsymmetrically
substituted
with
bulky
groups.
Despite
recent
advances,
only
very
few
catalytic
asymmetric
methods
have
been
developed
to
construct
such
axially
chiral
compounds.
We
describe
herein
a
dynamic
kinetic
resolution
approach
via
Brønsted
acid
catalyzed
atroposelective
transfer
hydrogenation
(ATH)
reaction
of
dicarbaldehydes
anilines.
The
desired
could
be
obtained
moderate
good
chemical
yields
(up
79
%)
high
enantioselectivities
95
%
ee)
under
standard
conditions.
Such
structural
motifs
interesting
precursors
for
further
transformations
potential
applications
synthesis
or
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Май 12, 2022
Abstract
Compared
with
the
well-developed
carbon-stereogenic
chemistry,
construction
of
boron-stereogenic
compounds
remains
undeveloped
and
challenging.
Herein,
previously
elusive
catalytic
enantioselective
has
been
achieved
through
desymmetric
B–H
bond
insertion
reaction.
The
reaction
2-arylpyridine-boranes
versatile
diazo
under
chiral
copper
catalyst
can
afford
good
to
excellent
enantioselectivity.
Moreover,
synthetic
utility
this
is
demonstrated
by
scalability
downstream
transformations.
DFT
calculations
provide
insights
into
mechanism
origin
stereoselectivity.
