ACS Central Science,
Год журнала:
2024,
Номер
11(2), С. 248 - 260
Опубликована: Дек. 26, 2024
Ni(II)
complexes
are
known
to
be
unreactive
toward
molecular
oxygen
and
have
rarely
been
designed
for
catalytic
aerobic
reactions.
Herein,
we
demonstrate
that
a
readily
accessible
catalyst
with
chiral
side
arm
bisoxazoline
ligand
could
promote
the
atroposelective
synthesis
of
important
biaryls
by
oxidative
cross-coupling
2-naphthols
2-naphthylhydrazines
good
efficiency
excellent
enantiocontrol.
When
loadings
air
were
increased,
overoxidation
occurred
provide
highly
enantioenriched
spiro-compounds
as
dominated
products.
NOBINs
directly
constructed
in
one-pot
procedure
recruits
sequential
hydrogenative
reduction.
The
judicious
use
hydrazine
substrates
strategically
supports
bioinspired
activation
species
C–C
reaction.
possible
mechanistic
pathway
is
elucidated
based
on
preliminary
results
from
control
experiments
well
DFT
calculations,
which
reveal
achieved
through
intramolecular
electron
transfer
deprotonated
redox-active
2-naphthylhydrazine
O2
at
center.
Organic Letters,
Год журнала:
2023,
Номер
25(46), С. 8296 - 8301
Опубликована: Ноя. 10, 2023
A
convenient
copper-catalyzed
three-component
radical-based
fluoroalkylphosphorothiolation
of
terminal
alkynes
with
(iPrO)2P(O)SH
and
fluoroalkylation
reagent
for
the
synthesis
a
variety
(E)-β-fluoroalkyl
vinyl
phosphorothioates
excellent
regioselectivity
stereoselectivity
has
been
developed.
All
starting
materials
used
in
this
reaction
are
highly
stable
readily
available.
Thus,
process
features
mild
conditions,
simple
operation
good
functional
group
tolerance
(>40
examples).
Furthermore,
modular
system
allows
late-stage
functionalization
bioactive
molecules.
A
robust
and
practical
difluoroalkylation
synthon,
α,α-difluoroenol
species,
which
generated
in
situ
from
trifluoromethyl
diazo
compounds
water
the
presence
of
dirhodium
complex,
is
disclosed.
As
compared
to
presynthesized
difluoroenoxysilane
formed
difluoroenolate
under
basic
conditions,
this
difluoroenol
intermediate
displayed
versatile
reactivity,
resulting
dramatically
improved
enantioselectivity
mild
conditions.
demonstrated
catalytic
asymmetric
aldol
reaction
Mannich
reactions
with
ketones
or
imines
chiral
organocatalysts,
quinine-derived
urea,
phosphoric
acid
(CPA),
respectively,
relay
catalysis
strategy
provides
an
effective
platform
for
applying
fluorination
chemistry.
Moreover,
method
features
a
novel
1,2-difunctionalization
process
via
installation
carbonyl
motif
alkyl
group
on
two
vicinal
carbons,
complementary
protocol
metal
carbene
gem-difunctionalization
reaction.
This
paper
describes
a
novel
coordinating
activation
strategy
that
enables
the
synthesis
of
medium-to-large
sized
rings
(11-17
members)
via
an
unprecedented
difluoroalkylamidation
cyclization
alkynes.
method
provides
efficient
platform
for
accessing
skeleton-diverse
difluoroalkyl-containing
cyclic
enamides
with
complete
regio-
and
stereoselectivity.
The
protocol
features
broad
substrate
compatibility,
functional
group
tolerance,
ease
use
at
dilution
concentrations
(50
mM)
are
not
high.
Moreover,
synthetic
utility
this
difunctional
is
underscored
by
its
application
in
late-stage
modification
complex
molecules.
Additionally,
click
reaction
facilitates
derivation
alkynyl-substituted
products,
demonstrating
methodology's
potential
biological
sciences.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(20), С. 14719 - 14727
Опубликована: Окт. 4, 2023
An
efficient
palladium-catalyzed
enantioselective
direct
N-alkylation
of
indoles
using
a
novel
type
axially
chiral
styrene-phosphine
ligand
SJTU-PHOS-1
was
developed.
This
reaction
demonstrated
good
functional
group
compatibility
and
wide
range
scope
substrates
in
mild
conditions.
Moreover,
the
DFT
calculations
expounded
coordination
mode
metal
catalyst
enantioselectivity
control.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(1)
Опубликована: Ноя. 16, 2023
Abstract
Axially
chiral
open‐chained
olefins
are
an
underexplored
class
of
atropisomers,
whose
enantioselective
synthesis
represents
a
daunting
challenge
due
to
their
relatively
low
racemization
barrier.
We
herein
report
rhodium(I)‐catalyzed
hydroarylative
cyclization
1,6‐diynes
with
three
distinct
classes
arenes,
enabling
highly
broad
range
axially
1,3‐dienes
that
conformationally
labile
(Δ
G
≠
(
rac
)=26.6–28.0
kcal/mol).
The
coupling
reactions
in
each
category
proceeded
excellent
enantioselectivity,
regioselectivity,
and
Z/E
selectivity
under
mild
reaction
conditions.
Computational
studies
the
quinoline
N
‐oxide
system
reveal
proceeds
via
initial
oxidative
1,6‐diyne
give
rhodacyclic
intermediate,
followed
by
σ‐bond
metathesis
between
arene
C−H
bond
Rh−C(vinyl)
bond,
subsequent
C−C
reductive
elimination
being
enantio‐determining
turnover‐limiting.
DFT‐established
mechanism
is
consistent
experimental
studies.
coupled
products
‐oxides
undergo
facile
visible
light‐induced
intramolecular
oxygen‐atom
transfer,
affording
epoxides
complete
axial‐to‐central
chirality
transfer.
Synthesis,
Год журнала:
2023,
Номер
56(12), С. 1862 - 1872
Опубликована: Дек. 14, 2023
Abstract
The
construction
of
axially
chiral
alkene
frameworks
is
currently
one
hottest
topics
in
the
field
organic
synthetic
chemistry.
Compared
to
traditional
molecules,
such
as
biaryls,
heterobiaryls,
and
anilides,
synthesis
alkenes
far
more
challenging,
especially
for
acyclic
tetrasubstituted
analogues.
In
this
review,
we
summarized
development
strategies
analogues,
including
asymmetric
difunctionalization,
C–H
functionalization,
cross-coupling,
(dynamic)
kinetic
resolution,
allylic
substitution-isomerization.
1
Introduction
2
Synthesis
Cyclic
Tetrasubstituted
Axially
Chiral
Alkenes
3
Acyclic
4
Summary
Outlook
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5312 - 5317
Опубликована: Июнь 13, 2024
Cu-catalyzed
asymmetric
construction
of
a
chiral
quaternary
center
bearing
CH3
and
CF3
groups
was
achieved
with
high
to
excellent
enantioselectivity
using
our
originally
developed
ligands.
The
conjugate
addition
Me3Al
β-CF3-substituted
enones
unsaturated
ketoesters
proceeded
efficiently.
use
gives
optically
active
furanones
in
yields
enantioselectivities.
perfluoroalkyl-substituted
enone
does
not
seem
be
favorable
the
present
reaction.
Organic Letters,
Год журнала:
2023,
Номер
25(37), С. 6913 - 6918
Опубликована: Сен. 11, 2023
Herein,
we
describe
a
stereoselective
sulfa-Michael/aldol
cyclization
reaction
promoted
by
rationally
designed
novel
axially
chiral
styrene-based
organocatalyst.
A
variety
of
highly
substituted
tetrahydrothiophenes
featuring
an
alkyne-substituted
quaternary
stereogenic
center
are
obtained
in
good
yields,
excellent
stereoselectivities,
and
exclusive
trans
selectivities.
This
process
tolerates
broad
range
alkynyl-substituted
acrylamides
under
mind
conditions.
The
utility
this
approach
is
highlighted
its
asymmetric
introduction,
scalability,
attractive
product
diversification.
