Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(16), P. 2798 - 2805
Published: April 13, 2023
It
remains
a
long-standing
challenge
to
directly
convert
alkynes
carboxylic
derivatives.
Herein,
unexpectedly
anti-Markovnikov
oxidation
of
unique
Au-allenylidene
pathway
instead
traditional
α-oxo
gold
carbene
routine
is
disclosed
for
in
situ
formation
and
transformation
highly
unsaturated
alkylidene
ketenes,
which
are
subsequently
trapped
by
broad
nucleophiles
such
as
alcohols,
phenols,
water,
amines,
sulfoximines
easily
access
α,β-unsaturated
drugs
natural
product
derivatives
multicomponent
reaction.
Based
on
this
scenario,
polyacrylate
polyacrylamide
efficiently
afforded
corresponding
polymerization.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(46), P. 21347 - 21355
Published: Nov. 11, 2022
The
first
copper-catalyzed
enantioselective
[4
+
1]
annulation
of
yne-allylic
esters
with
1,3-dicarbonyl
compounds
was
realized
through
an
elegant
remote
stereocontrol
strategy.
very
ε
regioselective
nucleophilic
substitution
developed
by
employing
a
novel
chiral
copper-vinylvinylidene
species
from
the
new
C4
synthon
esters.
Thus,
greatly
diverse
spirocycles
were
obtained
ample
scope
and
excellent
levels
chemo-,
regio-,
enantioselectivities.
Moreover,
detailed
mechanistic
studies
suggest
Conia-ene
cascade
pathway
on
stereochemical
induction
progress.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(52)
Published: Nov. 13, 2023
Impressive
progress
has
been
made
in
the
copper-catalyzed
asymmetric
propargylic
substitution
(APS)
reaction,
but
its
use
remote
yne-allylic
remains
a
challenging
topic.
Herein,
we
report
first
enantioselective
sulfonylation
of
esters
with
sodium
sulfinates.
The
reaction
is
assumed
to
occur
via
copper-vinylvinylidene
species
as
key
reactive
intermediate.
readily
available
starting
materials,
mild
conditions,
and
excellent
regio-,
enantio-
stereoselectivity,
well
broad
substrate
scope
(>70
examples),
show
practicality
attractiveness
this
method.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(47)
Published: Oct. 16, 2023
Abstract
Catalytic
asymmetric
transformations
by
dearomatization
have
developed
into
a
widely
applicable
synthetic
strategy,
but
heavily
relied
on
the
use
of
arenes
bearing
heteroatom.
In
this
case,
is
facilitated
involvement
p
‐orbital
electron
Different
from
conventional
substrate‐dependent
model,
here
we
demonstrate
that
activation
d
transition‐metal
center
can
serve
as
driving
force
for
dearomatization,
and
applied
to
development
novel
alkynyl
copper
remote
substitution
reaction.
A
newly
modified
PyBox
chiral
ligand
enables
construction
valuable
diarylmethyl
triarylmethyl
skeletons
in
high
enantioselectivities.
An
unexpected
tandem
process
involving
sequential
substitution/cyclization/1,5‐H
shift
leads
formation
enantioenriched
C−N
axis.
gram‐scale
reaction
various
downstream
highlight
robustness
method
potential
products.
Preliminary
mechanistic
studies
reveal
mononuclear
Cu‐catalyzed
process.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(6), P. 1843 - 1857
Published: Jan. 1, 2024
This
work
summarizes
recent
progress
in
nickel-catalyzed
propargylic
substitution
reactions,
categorizing
them
based
on
the
diverse
types
of
nucleophiles
involved,
with
a
specific
focus
exploring
asymmetric
transformations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(13)
Published: Jan. 26, 2023
Compared
to
γ-addition,
the
α-addition
of
α-branched
β,γ-unsaturated
aldehydes
faces
larger
steric
hindrance
and
disrupts
π-π
conjugation,
which
might
be
why
very
few
examples
are
reported.
In
this
article,
a
highly
diastereo-
enantioselective
α-regioselective
Mannich
reaction
isatin-derived
ketimines
with
α-,
β-
or
γ-branched
aldehydes,
generated
in
situ
from
Meinwald
rearrangement
vinyl
epoxides,
is
realized
by
using
chiral
N,N'-dioxide/ScIII
catalysts.
A
series
α-quaternary
allyl
homoallylic
alcohols
vicinal
multisubstituted
stereocenters
constructed
excellent
yields,
good
d.r.
ee
values.
Experimental
studies
DFT
(density
functional
theory)
calculations
reveal
that
large
ligand
Boc
(tButyloxy
carbonyl)
protecting
group
imines
critical
factors
for
α-regioselectivity.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(3), P. 690 - 695
Published: Dec. 5, 2023
A
reliable
protocol
for
asymmetric
Cu-catalyzed
alkynylallylic
dimethylamination
is
described
with
the
discovery
of
tetramethyldiaminomethane
as
a
new,
stable
and
convenient
surrogate
dimethylamine
nucleophile.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5758 - 5763
Published: July 1, 2024
Anthrones
are
key
structural
motifs
in
many
natural
products
and
pharmaceutical
chemicals.
However,
due
to
its
unique
tricyclic
aromatic
structure,
the
synthetic
space
for
development
of
chiral
anthrone
derivatives
is
largely
limited.
By
utilizing
potential
copper-catalyzed
remote
asymmetric
yne-allylic
substitution
reaction,
we
describe
first
example
highly
regio-
enantioselective
on
various
esters
with
anthrones
under
a
mild
reaction
condition,
which
afforded
range
enantioenriched
1,3-enynes
exhibiting
broad
functional
group
tolerance
across
51
examples.
