Chemical Communications,
Год журнала:
2023,
Номер
60(7), С. 831 - 834
Опубликована: Дек. 15, 2023
We
herein
report
regio-
and
enantioselective
arylation
of
β,γ-alkynyl-α-imino
esters
with
pyrroloisoquinolines.
Using
chiral
phosphoric
acid
catalysts,
a
wide
range
novel
axially
tetrasubstituted
α-amino
allenoates
were
accessed
in
good
yields
excellent
enantioselectivities.
Notably,
this
transformation
occurred
preferentially
at
the
sterically
more
hindered
C1-position
The
potential
scalability
late-stage
functionalization
demonstrated
utility
current
protocol.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(18), С. 10001 - 10006
Опубликована: Апрель 26, 2023
We
have
developed
a
new
three-component
catalytic
coupling
reaction
of
alkynyl
boronates,
diazomethanes,
and
aliphatic/aromatic
ketones
in
the
presence
BINOL
derivatives.
The
proceeds
with
remarkably
high
enantio-
diastereoselectivity
(up
to
three
contiguous
stereocenters)
affording
tertiary
CF3-allenols
single
operational
step.
under
mild,
neutral,
metal-free
conditions,
which
leads
level
functional
group
tolerance.
Organic Letters,
Год журнала:
2023,
Номер
25(36), С. 6654 - 6658
Опубликована: Сен. 6, 2023
A
novel
chiral
phosphoric
acid-catalyzed
tandem
regioselective
1,6-addition/double
intramolecular
nucleophilic
addition
annulation
of
the
propargylic
3-methyleneindoles
in
situ
generated
from
α-indolyl
alcohols
with
2-indolylmethanols
has
been
developed.
The
methodology
afforded
new
trifluoromethyl
pentalenobisindoles
bearing
an
all-carbon
quaternary
stereogenic
center
generally
good
yields
excellent
enantioselectivities.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(9), С. 2477 - 2484
Опубликована: Янв. 1, 2024
A
variety
of
optically
active
tertiary
propargylic
alcohols
and
tetrasubstituted
2,3-allenoic
acids
have
been
synthesized
via
a
Pd((
R
)-DTBM-SEGphos)Cl
2
-catalyzed
carboxylative
kinetic
resolution
reaction
racemic
alcohols.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Май 3, 2024
The
chemistry
of
quinone
methides
formed
in
situ
has
been
flourishing
recent
years.
In
sharp
contrast,
the
development
and
utilization
biphenyl
are
rare.
this
study,
we
achieved
a
remote
stereocontrolled
1,12-conjugate
addition
for
first
time.
presence
suitable
chiral
phosphoric
acid,
alkynyl
were
generated
from
α-[4-(4-hydroxyphenyl)phenyl]propargyl
alcohols,
followed
by
enantioselective
with
indole-2-carboxylates.
strategy
enabled
alcohols
to
serve
as
efficient
allenylation
reagents,
providing
practical
access
broad
range
axially
allenes
bearing
(1,1'-biphenyl)-4-ol
unit,
which
previously
less
accessible.
Combined
control
experiments,
density
functional
theory
calculations
shed
light
on
reaction
mechanism,
indicating
that
enantioselectivity
originates
nucleophilic
methides.
Notably,
not
only
versatile
intermediates
was
confirmed
but
also
organocatalytic
1,12-addition
established.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 27, 2024
Abstract
Radical‐involved
arylative
cross‐coupling
reactions
have
recently
emerged
as
an
attractive
strategy
to
access
valuable
aryl‐substituted
motifs.
However,
there
still
exist
several
challenges
such
limited
scope
of
radical
precursors/acceptors,
and
lack
general
asymmetric
catalytic
systems,
especially
regarding
the
multicomponent
variants.
Herein,
we
reported
a
copper‐Box
system
for
three‐component
vinylarenes
1,3‐enynes,
with
oxime
carbonates
aryl
boronic
acids.
The
proceed
under
practical
conditions
in
absence
or
presence
visible‐light
irradiation,
affording
chiral
1,1‐diarylalkanes,
benzylic
alkynes
allenes
good
enantioselectivities.
Mechanistic
studies
imply
that
copper/Box
complexes
play
dual
role
both
generation
ensuing
cross‐coupling.
In
cases
irradiation
could
improve
activity
complex
toward
initial
generation,
enabling
better
efficiency
match
between
formation
Chemical Science,
Год журнала:
2023,
Номер
14(44), С. 12676 - 12683
Опубликована: Янв. 1, 2023
An
unprecedented
nickel-catalysed
enantioselective
hydromonofluoromethylation
of
1,3-enynes
is
developed,
allowing
the
diverse
access
to
monofluoromethyl-tethered
axially
chiral
allenes,
including
challenging
deuterated
monofluoromethyl
(CD2F)-tethered
ones
that
are
otherwise
inaccessible.
It
represents
first
asymmetric
1,4-hydrofunctionalization
using
low-cost
nickel
catalysis,
thus
opening
a
new
avenue
for
activation
in
reaction
development.
The
utility
further
verified
by
its
broad
substrate
scope,
good
functionality
tolerance,
mild
conditions,
and
diversified
product
elaborations
toward
other
valuable
fluorinated
structures.
Mechanistic
experiments
DFT
calculations
provide
insights
into
mechanism
origin
enantioselectivity.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(5), С. 1078 - 1083
Опубликована: Янв. 17, 2024
Abstract
An
organocatalytic
remote
stereocontrolled
1,8‐conjugated
addition
of
in
situ
formed
propargylic
aza‐
p
‐QMs
from
α‐(4‐aminophenyl)
alcohols
and
indole‐2‐carboxylates
was
developed,
affording
axially
chiral
tetrasubstituted
allenes
62–99%
yield
with
52–99%
ee.
The
synthetic
strategy
not
only
enriches
the
chemistry
‐quinone
methides,
but
also
provides
an
alternative
tool
for
preparation
allenes.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(39)
Опубликована: Май 7, 2024
Axially
chiral
cycloalkylidenes
are
interesting
but
less
developed
axially
molecules.
Here,
a
bispidine-based
amine
catalytic
system
was
to
promote
efficiently
the
asymmetric
Knoevenagel
condensation
of
N-protected
oxindoles
and
benzofuranones
with
4-substituted
cyclohexanones.
A
variety
alkylidenecycloalkanes
stable
axial
chirality
were
obtained
in
good
yields
fairly
er
(enantiomeric
ratio).
Based
on
absolute
configuration
determination
product
DFT
calculations,
possible
mechanism
stereoselective
induction
proposed.
