Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(4)
Published: Nov. 22, 2022
Abstract
A
chiral
Brønsted
acid
catalysed
phosphine‐mediated
deoxygenation
protocol
is
reported.
This
metal‐free
method
provides
a
precise
kinetic
resolution
platform
for
azaarylethynyl
tertiary
alcohols,
which
are
broad
category
of
biologically
and
synthetically
important
azaarene
derivatives.
In
addition
to
providing
an
efficient
the
first
asymmetric
preparation
these
strategy
facilitates
construction
azaaryl‐functionalized
allenes
with
good
excellent
enantioselectivities.
The
high
selectivity
factors
(
s
up
235),
substrate
scope,
ability
convert
azaaryl
compounds
into
both
alcohols
robustly
underscore
efficiency
promising
utility
this
method.
practicability
further
validated
by
successful
synthesis
deuterated
ee
values
substantial
incorporation
deuterium
using
inexpensive
D
2
O
as
source.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(36)
Published: July 29, 2023
Abstract
An
efficient
and
straightforward
methodology
for
the
synthesis
of
1,2,2‐triarylethanones
2,2‐diarylethanones
has
been
developed,
via
a
visible
light‐promoted/Brønsted
acid‐catalyzed
carbonyl‐alkyne
metathesis/transfer
hydrogenation
one‐pot
reaction
benzoquinone,
arylalkyne,
Hantzsch
ester.
A
series
synthetically
useful
triarylethanones
diarylethanones
were
achieved
in
excellent
yield
under
mild
conditions.
This
protocol
is
operationally
simple,
photocatalyst‐free,
scalable
broad
substrate
scope.
Moreover,
this
involves
formation
three
chemical
bonds,
namely
C=O,
C−C,
C−H
bonds.
feature
enables
de
novo
2,2‐diarylethanones.
Additionally,
provides
convenient
practical
synthetic
route
tamoxifen.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(45)
Published: Sept. 19, 2023
Abstract
Chiral
α,α‐diaryl
ketones
are
structural
motifs
commonly
present
in
bioactive
molecules,
and
they
also
valuable
building
blocks
synthetic
organic
chemistry.
However,
catalytic
asymmetric
synthesis
of
bearing
a
tertiary
stereogenic
center
remains
largely
unsolved.
Herein,
we
report
de
novo
enantioselective
from
simple
alkynes
via
chiral
phosphoric
acid
(CPA)
catalysis.
A
broad
range
enolizable
prepared
good
yields
with
excellent
enantioselectivities.
The
described
protocol
serves
as
an
efficient
deuteration
method
for
the
preparation
enantiomerically
enriched
deuterated
ketones.
Using
methodology
reported,
including
one
best‐selling
anti‐breast
cancer
drugs,
tamoxifen,
readily
synthesized.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3878 - 3882
Published: April 28, 2024
The
synthesis
of
complex
alkanes
by
the
tetrafunctionalization
alkynes
is
limited
and
challenging.
Herein,
an
unprecedented
efficient
geminal
diazidation
dibromination
terminal
developed,
which
provides
novel
access
to
structurally
diverse
organic
azides.
approach
has
exclusive
chemo-
regioselectivity
features
mild
reaction
conditions,
good
tolerance
various
functional
groups,
more
crucially,
no
metal
involved
in
reaction,
thereby
benefiting
late-stage
decoration
medicinal
molecules.
A
mechanistic
study
showed
that
current
proceeds
via
a
radical
pathway.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(43)
Published: June 25, 2024
Abstract
We
herein
describe
the
first
example
of
ligand‐controlled,
copper‐catalyzed
regiodivergent
asymmetric
difunctionalization
terminal
alkynes
through
a
cascade
hydroboration
and
hydroallylation
process.
The
catalytic
system,
consisting
(
R
)‐DTBM‐Segphos
CuBr,
could
efficiently
achieve
1,1‐difunctionalization
aryl
alkynes,
while
ligand
switching
to
S,S
)‐Ph‐BPE
result
in
1,2‐difunctionalization
exclusively.
In
addition,
alkyl
substituted
especially
industrially
relevant
acetylene
propyne,
were
also
valid
feedstocks
for
1,1‐difunctionalization.
This
protocol
is
characterized
by
good
functional
group
tolerance,
broad
scope
substrates
(>150
examples),
mild
reaction
conditions.
showcase
value
this
method
late‐stage
functionalization
complicated
bioactive
molecules
simplifying
synthetic
routes
toward
key
intermediacy
natural
product
(bruguierol
A).
Mechanistic
studies
combined
with
DFT
calculations
provide
insight
into
mechanism
origins
ligand‐controlled
regio‐
stereoselectivity.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(4)
Published: Nov. 22, 2022
Abstract
A
chiral
Brønsted
acid
catalysed
phosphine‐mediated
deoxygenation
protocol
is
reported.
This
metal‐free
method
provides
a
precise
kinetic
resolution
platform
for
azaarylethynyl
tertiary
alcohols,
which
are
broad
category
of
biologically
and
synthetically
important
azaarene
derivatives.
In
addition
to
providing
an
efficient
the
first
asymmetric
preparation
these
strategy
facilitates
construction
azaaryl‐functionalized
allenes
with
good
excellent
enantioselectivities.
The
high
selectivity
factors
(
s
up
235),
substrate
scope,
ability
convert
azaaryl
compounds
into
both
alcohols
robustly
underscore
efficiency
promising
utility
this
method.
practicability
further
validated
by
successful
synthesis
deuterated
ee
values
substantial
incorporation
deuterium
using
inexpensive
D
2
O
as
source.
