Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 15, 2023
Abstract
Asymmetric
cross‐couplings
based
on
1,2‐carbon
migration
from
B‐ate
complexes
have
been
developed
efficiently
to
access
valuable
organoboronates.
However,
enantioselective
reactions
triggered
by
1,2‐boron
shift
remained
be
unaddressed
synthetic
challenge.
Here,
Ir‐catalyzed
asymmetric
allylic
alkylation
enabled
was
developed.
In
this
reaction,
we
disclosed
that
excellent
enantioselectivities
were
achieved
through
an
interesting
dynamic
kinetic
resolution
(DKR)
process
of
carbonates
at
the
elevated
temperature.
Notably,
highly
(bis‐boryl)alkenes
array
diversifications
versatile
molecules.
Extensive
experimental
and
computational
studies
conducted
elucidate
reaction
mechanism
DKR
clarify
origin
enantioselectivities.
ACS Catalysis,
Год журнала:
2021,
Номер
11(15), С. 9151 - 9158
Опубликована: Июль 9, 2021
In
this
report,
distally
disposed
axial
and
central
chirality
has
been
installed
in
a
synergistic
fashion
via
rhodium-catalyzed
C–H
alkylation
of
benzamides
using
N-arylmaleimide
as
the
alkylating
reagent,
which
enantio-
diastereo-determining
steps
are
merged
into
single
one.
The
coupling
system
features
mild
reaction
conditions,
broad
substrate
scope,
excellent
diastereoselectivity.
chiral
induction
enabled
by
judicious
choice
rhodium
cyclopentadienyl
catalyst
that
serves
to
control
both
orientation
olefin
unit
prochiral
C–N
bond.
Catalysis Science & Technology,
Год журнала:
2022,
Номер
12(13), С. 4100 - 4112
Опубликована: Янв. 1, 2022
This
minireview
describes
the
recent
progress
of
iridium-catalyzed
enantioselective
allylic
substitution
using
phosphoramidite-alkene
ligands
realizing
highly
carbon–carbon
and
carbon–heteroatom
bond
formation.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(10)
Опубликована: Янв. 4, 2023
Herein,
we
report
a
synthesis
of
cyclohexanones
bearing
multi-continuous
stereocenters
by
combining
copper-catalyzed
asymmetric
conjugate
addition
dialkylzinc
reagents
to
cyclic
enones
with
iridium-catalyzed
allylic
substitution
reaction.
Good
excellent
yields,
diastereoselectivity
and
enantioselectivity
can
be
obtained.
Unlike
the
stereodivergent
construction
adjacent
(1,2-position)
reported
in
literature,
current
reaction
achieve
nonadjacent
(1,3-position)
proper
combination
two
chiral
catalysts
different
enantiomers.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(15), С. 8275 - 8284
Опубликована: Апрель 5, 2023
Allyl
carboxylates
are
useful
synthetic
intermediates
in
a
variety
of
organic
transformations,
including
catalytic
nucleophilic/electrophilic
allylic
substitution
reactions
and
1,2-difunctionalization
reactions.
However,
the
1,3-difunctionalization
allyl
remains
elusive.
Herein,
we
report
first
photoinduced,
phosphine-catalyzed
1,3-carbobromination
carboxylates,
affording
range
valuable
substituted
isopropyl
(sIPC).
The
transformation
has
broad
functional
group
tolerance,
is
amenable
to
late-stage
modification
complex
molecules
gram-scale
synthesis,
expands
reaction
profiles
phosphine
catalysis.
Preliminary
experimental
computational
studies
suggest
non-chain-radical
mechanism
involving
formation
an
electron
donor-acceptor
complex,
1,2-radical
migration
(RaM),
Br-atom
transfer
processes.
We
anticipate
that
1,2-RaM
reactivity
radical
will
both
serve
as
platform
for
development
new
transformations
synthesis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 15, 2023
Abstract
Asymmetric
cross‐couplings
based
on
1,2‐carbon
migration
from
B‐ate
complexes
have
been
developed
efficiently
to
access
valuable
organoboronates.
However,
enantioselective
reactions
triggered
by
1,2‐boron
shift
remained
be
unaddressed
synthetic
challenge.
Here,
Ir‐catalyzed
asymmetric
allylic
alkylation
enabled
was
developed.
In
this
reaction,
we
disclosed
that
excellent
enantioselectivities
were
achieved
through
an
interesting
dynamic
kinetic
resolution
(DKR)
process
of
carbonates
at
the
elevated
temperature.
Notably,
highly
(bis‐boryl)alkenes
array
diversifications
versatile
molecules.
Extensive
experimental
and
computational
studies
conducted
elucidate
reaction
mechanism
DKR
clarify
origin
enantioselectivities.
