Organic Letters,
Год журнала:
2024,
Номер
26(21), С. 4443 - 4450
Опубликована: Май 21, 2024
Highly
functionalized
organic
molecules
are
in
high
demand,
but
their
preparation
is
challenging.
Copper-catalyzed
transformation
of
alkynyl-
and
allenyl-containing
substrates
has
emerged
as
a
powerful
tool
to
achieve
this
objective.
Herein,
an
efficient
copper-catalyzed
difunctionalization
propargylic
carbonates
through
tandem
nucleophilic
substitution/boroprotonation
been
developed,
affording
the
formation
thiol-,
selenium-,
boron-functionalized
alkenes
with
yield
stereoselectivity.
Two
distinct
catalytic
mechanisms
involving
single
reaction
without
any
requirement
catalyst
change
were
successfully
demonstrated.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(47)
Опубликована: Окт. 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.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
364(3), С. 565 - 573
Опубликована: Окт. 29, 2021
Abstract
Rh(I)‐catalyzed
decarboxylative
arylation
of
alkynyl
cyclic
carbonates
using
commercially
available
and
low‐toxic
aryl
boronic
acids
has
been
disclosed.
Depending
on
the
nature
carbonates,
methodology
provides
a
straightforward
platform
to
access
either
substituted
2,3‐allenols
or
1,3‐butadiene
derivatives.
Internal
undergo
monoarylation
conveniently
afford
with
high
syn
‐selectivity
for
hydroxy
groups.
Whereas,
terminal
led
formation
diarylated
derivatives
having
cis
‐configuration
two
groups
via
allenyl
rhodium(I)alkoxide
intermediate.
The
compatibility
various
functional
allowed
develop
library
diversely
functionalized
scaffolds
excellent
regioselectivity
in
good
yields.
Late‐stage
transformation
series
natural
products
highlights
wide
applicability
process.
Additionally,
scale‐up
experiments
downstream
transformations
α
‐allenol
into
other
valuable
heterocycles
illustrate
efficacy
protocol.
magnified
image
Angewandte Chemie,
Год журнала:
2023,
Номер
135(14)
Опубликована: Фев. 10, 2023
Abstract
Transition‐metal‐catalysed
reactions
of
cyclic
ethynylethylene
carbonates
have
been
intensively
studied
because
their
robustness
in
new
bond
formation
and
diversified
molecule
construction.
Known
reaction
modes
usually
involve
a
substitution
step
occurring
at
either
the
propargylic
or
terminal
alkyne
positions.
Here,
we
report
an
unprecedented
pattern
which
first
undergo
rearrangement
to
release
allenal
intermediates,
subsequently
react
with
diverse
nucleophiles
furnish
synthetically
useful
allylic
allenols,
phosphorus
ylides,
cyclopropylidene
ketones
through
addition
process
rather
than
pathway.
The
products
enable
various
further
transformations,
mechanistic
studies
theoretical
calculations
reveal
that
does
not
proceed
via
semipinacol
type
[1,2]‐hydride
shift,
but
base‐mediated
deprotonation
as
key
induce
rearrangement.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(25)
Опубликована: Апрель 9, 2024
Abstract
A
formal
[4+2]
cycloaddition
reaction
of
ethynylethylene
carbonates
and
2‐aminophenols
has
been
developed
for
the
synthesis
3,4‐dihydro‐2
H
‐benzo[
b
][1,4]oxazines
bearing
quaternary
carbon
atoms.
The
features
mild
conditions,
good
functional
group
compatibility
yields.
Furthermore,
when
using
chiral
PyBox
ligand,
this
strategy
could
also
achieve
asymmetric
][1,4]oxazines.
Application
studies
indicated
that
hydroxymethyl
final
products
was
an
excellent
can
be
further
modified
easily.
Organic Letters,
Год журнала:
2024,
Номер
26(21), С. 4443 - 4450
Опубликована: Май 21, 2024
Highly
functionalized
organic
molecules
are
in
high
demand,
but
their
preparation
is
challenging.
Copper-catalyzed
transformation
of
alkynyl-
and
allenyl-containing
substrates
has
emerged
as
a
powerful
tool
to
achieve
this
objective.
Herein,
an
efficient
copper-catalyzed
difunctionalization
propargylic
carbonates
through
tandem
nucleophilic
substitution/boroprotonation
been
developed,
affording
the
formation
thiol-,
selenium-,
boron-functionalized
alkenes
with
yield
stereoselectivity.
Two
distinct
catalytic
mechanisms
involving
single
reaction
without
any
requirement
catalyst
change
were
successfully
demonstrated.
