Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(30)
Опубликована: Май 25, 2023
Abstract
Hydrofunctionalization
of
alkynes
is
one
the
most
efficient
ways
to
access
axially
chiral
styrenes
with
open‐chained
olefins.
While
great
advances
have
been
achieved
for
1‐alkynylnaphthalen‐2‐ols
and
analogues,
atroposelective
hydrofunctionalization
unactivated
internal
lags.
Herein
we
reported
a
platinum‐catalyzed
hydrosilylation
first
time.
With
monodentate
TADDOL‐derived
phosphonite
L1
used
as
ligand,
various
were
in
excellent
enantioselectivities
high
E
‐selectivities.
Control
experiments
showed
that
N
H‐arylamide
groups
significant
effects
on
both
yields
could
act
directing
groups.
The
potential
utilities
products
shown
by
transformations
amide
motifs
products.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(35), С. 14025 - 14040
Опубликована: Авг. 25, 2021
Transition-metal-catalyzed
enantioselective
C-H
functionalization
has
become
a
powerful
strategy
for
the
formation
of
C-C
or
C-X
bonds,
enabling
highly
asymmetric
synthesis
wide
range
enantioenriched
compounds.
Atropisomers
are
widely
found
in
natural
products
and
pharmaceutically
relevant
molecules,
have
also
applications
as
privileged
frameworks
chiral
ligands
catalysts.
Thus,
research
into
routes
atropisomers
garnered
great
interest
recent
years.
In
this
regard,
transition-metal-catalyzed
emerged
an
atom-economic
efficient
toward
their
synthesis.
Perspective,
approaches
by
reactions
summarized.
The
main
focus
here
is
on
catalysis
via
Pd,
Rh,
Ir
complexes,
which
been
most
frequently
utilized
catalysts
among
reported
reactions.
Finally,
we
discuss
limitations
available
protocols
give
outlook
possible
future
avenues
research.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(31), С. 12335 - 12344
Опубликована: Авг. 3, 2021
The
efficient
stereoselective
synthesis
of
conjugated
dienes,
especially
those
with
axial
chirality,
remains
a
great
challenge.
Herein,
we
report
the
highly
atroposelective
axially
chiral
styrenes
1,3-diene
scaffold
via
Pd(II)-catalyzed
thioether-directed
alkenyl
C-H
olefination
strategy.
This
strategy
features
easy
operation,
mild
reaction
conditions,
high
functional
group
tolerance
(69
examples),
complete
Z-selectivity,
and
excellent
enantioselectivities
(up
to
99%
ee).
Notably,
enantioselective
atropisomers
two
stereogenic
axes
were
also
achieved
using
this
ee
97:3
dr).
Moreover,
could
be
scaled
up,
resulting
easily
oxidized
into
sulfoxide
derivatives
diastereoselectivities,
which
showed
promise
as
new
type
sulfur-olefin
ligand.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Фев. 28, 2022
Abstract
Biaryl
scaffolds
are
found
in
natural
products
and
drug
molecules
exhibit
a
wide
range
of
biological
activities.
In
past
decade,
the
transition
metal-catalyzed
C–H
arylation
reaction
came
out
as
an
effective
tool
for
construction
biaryl
motifs.
However,
traditional
reactions
have
limitations
like
harsh
conditions,
narrow
substrate
scope,
use
additives
etc.
therefore
encouraged
synthetic
chemists
to
look
alternate
greener
approaches.
This
review
aims
draw
general
overview
on
bond
formation
C–C
bonds
with
aid
different
methodologies,
majorly
highlighting
sustainable
Tetrahedron Chem,
Год журнала:
2022,
Номер
1, С. 100009 - 100009
Опубликована: Март 1, 2022
Axial
chirality
is
historically
epitomized
by
biaryl
compounds
containing
rotationally
impeded
aryl-aryl
linkage.
As
the
field
of
atroposelective
catalysis
advances,
synthesis
and
application
less
common
scaffolds
such
as
alkenes
have
now
come
to
fore.
The
manifestation
axial
in
aryl
was
hypothesized
1928
first
resolution
achieved
nearly
a
decade
later.
However,
catalytic
asymmetric
construction
axially
chiral
open-chain
appeared
only
2017
which
ushered
renewed
focus
on
these
structures.
In
principle,
possess
an
alkene
group
tethered
at
one
end
stereogenic
axis,
greatly
reduces
overall
rigidity.
To
date,
atropisomers
with
C
(vinyl)-C
(aryl)
(vinyl)-heteroatom
bond
been
reported.
Considering
rapid
growth
synthetic
utility
alkenes,
this
review
intends
provide
historical
overview
discusses
new
developments.
It
hope
that
timely
discussion
would
motivate
continued
nascent
field.
Chemical Reviews,
Год журнала:
2023,
Номер
123(17), С. 10641 - 10727
Опубликована: Авг. 28, 2023
Enantiomers,
where
chirality
arises
from
restricted
rotation
around
a
single
bond,
are
atropisomers.
Due
to
the
unique
nature
of
origins
their
chirality,
synthetic
strategies
access
these
compounds
in
an
enantioselective
manner
differ
those
used
prepare
enantioenriched
containing
point
arising
unsymmetrically
substituted
carbon
center.
In
particular
stereodynamic
transformations,
such
as
dynamic
kinetic
resolutions,
thermodynamic
and
deracemizations,
which
rely
on
ability
racemize
or
interconvert
enantiomers,
promising
set
transformations
optically
pure
late
stage
sequence.
Translation
approaches
with
atropisomers
requires
expanded
toolbox
for
epimerization/racemization
provides
opportunity
develop
new
conceptual
framework
synthesis
compounds.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(28), С. 15510 - 15516
Опубликована: Апрель 16, 2021
Abstract
Chiral
cyclopentadienyl
rhodium
(CpRh)
complex‐catalyzed
asymmetric
C−H
functionalization
reactions
have
witnessed
a
significant
progress
in
organic
synthesis.
In
sharp
contrast,
the
reported
chiral
Cp
ligands
are
limited
to
C‐linked
and
often
synthetically
challenging.
To
address
these
issues,
we
developed
novel
class
of
tunable
bearing
oxygen
linkers,
which
were
efficient
catalysts
for
arylation
benzo[
h
]quinolines
with
1‐diazonaphthoquinones,
affording
axially
heterobiaryls
excellent
yields
enantioselectivity
(up
99
%
yield,
98.5:1.5
er).
Mechanistic
studies
suggest
that
reaction
is
likely
proceed
by
electrophilic
activation,
followed
coupling
cyclometalated
rhodium(III)
complex
1‐diazonaphthoquinones.
