Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(39)
Опубликована: Июнь 20, 2023
The
development
of
catalytic
asymmetric
reaction
with
water
as
the
reactant
is
challenging
due
to
reactivity-
and
stereoselectivity-control
issues
resulted
from
low
nucleophilicity
small
size
water.
We
disclose
herein
a
chiral
phosphoric
acid
(CPA)
catalyzed
atroposelective
ring-opening
biaryl
oxazepines
A
series
undergo
CPA
hydrolysis
in
highly
enantioselective
manner.
key
for
success
this
use
new
SPINOL-derived
catalyst
high
reactivity
oxazepine
substrates
towards
under
acidic
conditions.
Density
functional
theory
calculations
suggest
that
proceeds
via
dynamic
kinetic
resolution
pathway
addition
imine
group
both
enantio-
rate-determining.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(49), С. 26747 - 26755
Опубликована: Ноя. 29, 2023
Herein,
we
report
a
cobalt-catalyzed
atroposelective
reductive
cross-coupling
of
racemic
heterobiaryl
tosylates
with
C(sp2)–X
type
electrophile.
Both
aryl
and
alkenyl
halides
are
competent
precursors
for
this
reaction,
providing
variety
heterobiaryls
as
the
products
in
highly
enantioselective
manner
high
functionality
tolerance.
The
related
asymmetric
arylation
alkenylation
discovered
to
proceed
divergent
mechanisms.
reaction
pathway
changes
from
kinetic
resolution
(KR)
when
bromides
iodides
bearing
strong
electron-withdrawing
substitution
on
para-position
employed
starting
materials
an
enantioconvergent
transformation
via
dynamic
KR
configurationally
labile
cobaltacycles
relatively
electron-rich
used.
change
mechanisms
turns
out
arise
relative
rates
two
competing
elementary
steps,
which
epimerization
cyclic
Co(I)
intermediates
their
trapping
by
coupling
electrophiles
C(sp2)-type
oxidative
addition.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(29), С. 15721 - 15728
Опубликована: Июль 11, 2023
Herein,
a
protocol
for
enantioconvergent
transformation
of
anisole
derivatives
is
disclosed
via
nickel-catalyzed
dynamic
kinetic
asymmetric
cross-coupling
the
C(Ar)–OMe
bond.
Versatile
axially
chiral
heterobiaryls
are
successfully
assembled.
Synthetic
transformations
demonstrate
application
potential
this
method.
Mechanistic
studies
indicate
that
enantioconvergence
might
be
accessed
through
ligand-controlled
epimerization
diastereomeric
5-membered
aza-nickelacycle
species
rather
than
conventional
resolution.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 15, 2024
Axially
chiral
biaryl
δ-amino
acids
possess
significantly
different
conformational
properties
and
environment
from
centrally
amino
acids,
therefore,
have
drawn
considerable
attention
in
the
fields
of
synthetic
medicinal
chemistry.
Herein,
a
novel
phenanthroline-potassium
catalyst
has
been
developed
by
constructing
well-organized
axially
ligand
composed
one
1,10-phenanthroline
unit
two
1,1'-bi-2-naphthol
(BINOL)
units.
In
presence
this
catalyst,
good
to
excellent
yields
enantioselectivities
(up
99
%
yield,
98
:
2
er)
achieved
ring-opening
alcoholytic
dynamic
kinetic
resolution
variety
lactams,
thereby
providing
an
efficient
protocol
for
catalytic
asymmetric
synthesis
unnatural
acid
derivatives.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 24, 2024
Controlling
the
cross-coupling
reaction
between
two
different
radicals
is
a
long-standing
challenge
due
to
process
occurring
statistically,
which
would
lead
three
products,
including
homocoupling
products
and
one
product.
Generally,
selectivity
achieved
by
persistent
radical
effect
(PRE)
that
requires
presence
of
transient
radical,
thus
resulting
in
limited
precursors.
In
this
paper,
highly
selective
alkyl
with
acyl
construct
C(sp
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(39)
Опубликована: Июнь 20, 2023
The
development
of
catalytic
asymmetric
reaction
with
water
as
the
reactant
is
challenging
due
to
reactivity-
and
stereoselectivity-control
issues
resulted
from
low
nucleophilicity
small
size
water.
We
disclose
herein
a
chiral
phosphoric
acid
(CPA)
catalyzed
atroposelective
ring-opening
biaryl
oxazepines
A
series
undergo
CPA
hydrolysis
in
highly
enantioselective
manner.
key
for
success
this
use
new
SPINOL-derived
catalyst
high
reactivity
oxazepine
substrates
towards
under
acidic
conditions.
Density
functional
theory
calculations
suggest
that
proceeds
via
dynamic
kinetic
resolution
pathway
addition
imine
group
both
enantio-
rate-determining.
