Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 18, 2025
We
report
a
chiral
phosphoric
acid-catalyzed
hydrolytic
parallel
kinetic
resolution
(HPKR)
of
racemic
epoxides
and
activated
alcohols.
Using
an
acyloxy-assisted
activation
strategy,
this
method
enables
the
highly
stereocontrolled
hydrolysis
under
mild
conditions.
A
wide
range
aryl-substituted
secondary
alcohols
were
effectively
transformed,
providing
corresponding
with
combined
yields
up
to
99%
enantiomeric
ratios
exceeding
99:1.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(14), P. 8443 - 8448
Published: June 25, 2021
A
practical
method
for
kinetic
resolution
of
α-tertiary
propargylic
amines
has
been
achieved
via
asymmetric
remote
aminations
anilines
with
azodicarboxylates
enabled
by
chiral
phosphoric
acid
catalysis.
broad
range
aryl
and
alkyl
groups
at
the
α-position,
as
well
substituted
alkynyl
N-aryl
were
tolerated
in
these
reactions,
providing
high
performances
(with
an
s-factor
up
to
111).
In
addition,
bearing
α-CN
group
(the
Strecker
reaction
product)
could
be
kinetically
resolved
excellent
stereoselectivity
under
same
conditions.
Fruitful
transformations
amination
products
recovered
demonstrated
power
this
synthesis
their
derivatives.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(23), P. 14609 - 14618
Published: Nov. 15, 2022
Enantio-enriched
9,10-dihydroacridines
are
useful
chiral
N-heterocycles
in
many
aspects;
however,
their
asymmetric
catalytic
synthesis
is
rather
challenging,
as
the
stereocenter
remote
to
functional
group.
Herein,
we
disclose
an
efficient
enantioselective
desymmetrization
protocol
through
aromatic
aminations
enabled
by
a
new
type
of
spirocyclic
phosphoric
acid
(CPA)
catalyst,
which
gave
access
wide
range
dihydroacridines
bearing
9,9-disubstitutions
with
extremely
broad
scope
(compatible
both
aryl,alkyl-
and
dialkyl-substitutions)
excellent
enantioselectivities
(up
>99%
ee).
In
addition,
this
method
was
also
applicable
construction
stereogenic
silicon
center
kinetic
resolution
unsymmetrical
dihydroacridine
derivatives.
Density
theory
calculations
were
performed
elucidate
origin
regio-
enantioselectivity
these
reactions,
arose
from
skeletons
bulky
polyaromatic
substitutions
CPA
catalyst.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(21), P. 7975 - 7981
Published: Jan. 1, 2024
An
efficient
protocol
for
the
asymmetric
synthesis
of
fluorenols
has
been
developed
through
an
enantioconvergent
process
enabled
by
Pd(ii)/chiral
norbornene
cooperative
catalysis.
This
approach
allows
facile
access
to
diverse
functionalized
chiral
with
constantly
excellent
enantioselectivities,
applying
readily
available
racemic
secondary
ortho-bromobenzyl
alcohols
and
aryl
iodides
as
starting
materials.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(37)
Published: May 7, 2024
The
development
of
methods
to
allow
the
selective
acylative
dynamic
kinetic
resolution
(DKR)
tetra-substituted
lactols
is
a
recognised
synthetic
challenge.
In
this
manuscript,
highly
enantioselective
isothiourea-catalysed
DKR
morpholinone
and
benzoxazinone-derived
reported.
scope
limitations
methodology
have
been
developed,
with
high
enantioselectivity
good
excellent
yields
(up
89
%,
99
:
1
er)
observed
across
broad
range
substrate
derivatives
incorporating
substitution
at
N(4)
C(2),
di-
spirocyclic
C(5)
C(6),
as
well
benzannulation
(>35
examples
in
total).
process
amenable
scale-up
on
g
laboratory
scale.
factors
leading
selectivity
probed
through
computation,
an
N-C=O⋅⋅⋅isothiouronium
interaction
identified
key
producing
ester
products
enantioenriched
form.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 18, 2025
We
report
a
chiral
phosphoric
acid-catalyzed
hydrolytic
parallel
kinetic
resolution
(HPKR)
of
racemic
epoxides
and
activated
alcohols.
Using
an
acyloxy-assisted
activation
strategy,
this
method
enables
the
highly
stereocontrolled
hydrolysis
under
mild
conditions.
A
wide
range
aryl-substituted
secondary
alcohols
were
effectively
transformed,
providing
corresponding
with
combined
yields
up
to
99%
enantiomeric
ratios
exceeding
99:1.
