Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(26)
Published: April 27, 2023
Abstract
We
herein
describe
a
palladium‐catalyzed
hydrocyanation
of
propiolamides
for
the
stereodivergent
synthesis
trisubstituted
acrylonitriles.
This
synthetic
method
tolerated
various
primary,
secondary
and
tertiary
propiolamides.
The
cautious
selection
suitable
ligand
is
essential
to
success
this
process.
Control
experiments
indicate
intermediacy
E
‐acrylonitriles,
which
lead
Z
‐acrylonitriles
via
isomerization.
density
functional
theory
calculations
suggests
that
bidentate
L2
enables
feasible
cyclometallation/isomerization
pathway
isomerization,
while
monodentate
L1
inhibits
leading
divergent
stereoselectivity.
usefulness
can
be
demonstrated
by
readily
derivatization
products
give
E‐
‐trisubstituted
alkenes.
In
addition,
‐
‐acrylonitrile
have
also
been
successfully
employed
in
cycloaddition
reactions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(32), P. 17557 - 17563
Published: Aug. 4, 2023
Alkenes
are
ubiquitous
in
organic
chemistry,
yet
many
classes
of
alkenes
remain
challenging
to
access
by
current
synthetic
methodology.
Herein,
we
report
a
copper
hydride-catalyzed
approach
for
the
synthesis
Z-configured
trisubstituted
with
high
stereo-
and
regioselectivity
via
alkyne
hydroalkylation.
A
DTBM-dppf-supported
Cu
catalyst
was
found
be
optimal,
providing
substantial
increase
product
yield
compared
reactions
conducted
dppf
as
ligand.
DFT
calculations
show
that
DTBM
substitution
leads
acceleration
hydrocupration
through
combined
ground
transition
state
effects
related
preventing
dimerization
enhancing
catalyst–substrate
dispersion
interactions,
respectively.
Alkyne
hydroalkylation
successfully
demonstrated
methyl
larger
alkyl
tosylate
electrophiles
produce
variety
(hetero)aryl-substituted
moderate
yields
complete
selectivity
Z
stereochemically
configured
products.
In
formation
key
C–C
bond,
computational
studies
revealed
direct
SN2
pathway
alkylation
vinylcopper
intermediate
situ-formed
iodides.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(18), P. 2426 - 2446
Published: Aug. 29, 2023
ConspectusIn
this
Account,
we
share
the
story
of
development
catalytic
olefin
metathesis
processes
that
efficiently
deliver
a
wide
range
acyclic
and
macrocyclic
E-
or
Z-trisubstituted
alkenes.
The
tale
starts
with
us
unveiling,
in
collaboration
Richard
Schrock
his
team,
blueprint
2009
for
design
kinetically
controlled
Z-selective
reactions.
This
paved
way
Mo-,
W-,
Ru-based
catalysts
strategies
synthesizing
countless
linear
Z-olefins.
Six
years
later,
2015,
found
abundant
Z-alkene
feedstocks,
such
as
oleic
acid,
can
be
directly
transformed
to
high-value
more
difficult-to-access
alkenes
through
cross-metathesis
reaction
promoted
by
Ru-catechothiolate
complex
had
developed;
approach,
later
coined
stereoretentive
metathesis,
was
extended
synthesis
E-alkenes.It
all
about
disubstituted
until
when
2017
addressed
challenge
accessing
stereodefined
Z-
E-trisubstituted
alkenes,
key
medicine
materials
research.
These
transformations
most
effectively
catalyzed
Mo
monoaryloxides
pyrrolide
(MAP)
chloride
(MAC)
complexes.
A
central
aspect
advance
is
merging
which
delivered
trisubstituted
alkenyl
fluorides,
chlorides,
bromides
cross-coupling.
used
various
combinations,
thereby
enabling
access
assorted
alkene.
Ensuing
work
led
emergence
other
involving
substrates
purchased
high
stereoisomeric
purity,
notably
Z-trihalo
Trisubstituted
olefins,
Z
E,
bearing
chemoselectively
stereoretentively
alterable
F,Cl-terminus
B(pin),Cl-terminus
may,
thus,
easily
reliably
synthesized.
Methods
preparation
bromide
regioisomers
α,β-unsaturated
carboxylic
thiol
esters,
nitriles,
acid
fluorides
followed,
along
ring-closing
reactions
afford
olefins.
E-Macrocyclic
including
those
contain
little
no
entropic
support
cyclization
(minimally
functionalized)
and/or
are
disfavored
under
substrate-controlled
conditions,
now
utility
latest
chapter
history
has
been
highlighted
applications
several
biologically
active
compounds,
well
their
analogues,
marked
one
site-specifically
incorporated
fluorine
atoms
but
higher
energy
otherwise
unobtainable
conformers.The
investigations
discussed
here,
represent
every
method
reported
thus
far
preparing
olefin,
underscore
inimitable
power
Mo-based
catalysts.
Account
also
showcases
variety
mechanistic
attributes─some
first
time,
each
instrumental
solving
problem.
Extensive
knowledge
nuances
will
needed
if
address
successfully
next
challenging
problem,
namely,
may
synthesize
tetrasubstituted
especially
readily
modifiable,
purity.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: April 27, 2023
We
herein
describe
a
palladium-catalyzed
hydrocyanation
of
propiolamides
for
the
stereodivergent
synthesis
trisubstituted
acrylonitriles.
This
synthetic
method
tolerated
various
primary,
secondary
and
tertiary
propiolamides.
The
cautious
selection
suitable
ligand
is
essential
to
success
this
process.
Control
experiments
indicate
intermediacy
E-acrylonitriles,
which
lead
Z-acrylonitriles
via
isomerization.
density
functional
theory
calculations
suggests
that
bidentate
L2
enables
feasible
cyclometallation/isomerization
pathway
E
Z
isomerization,
while
monodentate
L1
inhibits
leading
divergent
stereoselectivity.
usefulness
can
be
demonstrated
by
readily
derivatization
products
give
E-
Z-trisubstituted
alkenes.
In
addition,
Z-acrylonitrile
have
also
been
successfully
employed
in
cycloaddition
reactions.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
Substituted
alkenes,
crucial
in
organic
chemistry,
are
typically
accessed
from
internal
alkynes
by
using
transition-metal
catalysis.
Herein,
we
report
a
novel
approach
to
the
Lewis
acid-catalyzed
synthesis
of
trisubstituted
alkenes
bearing
quaternary
carbon
alkynols
and
2-pyrrolyl
arylamines.
This
method
involves
allene
formation
followed
intramolecular
[5
+
1]
annulation
furnish
diverse
range
with
excellent
regioselectivity
poor
diastereoselectivity.
Further,
demonstrated
gram-scale
synthetic
transformations
proposed
reaction
mechanism
based
on
isolation
intermediates.
Science,
Journal Year:
2024,
Volume and Issue:
386(6718), P. 167 - 175
Published: Oct. 10, 2024
Polycyclic
polyprenylated
acylphloroglucinols
(PPAPs)
are
a
class
of
>400
natural
products
with
broad
spectrum
bioactivity,
ranging
from
antidepressant
and
antimicrobial
to
anti-obesity
anticancer
activity.
Here,
we
present
scalable,
regio-,
site-,
enantioselective
catalytic
method
for
synthesis
cyclic
β-prenyl
ketones,
compounds
that
can
be
used
efficient
syntheses
many
PPAPs
in
high
enantiomeric
purity.
The
transformation
is
prenyl
conjugate
addition
β-ketoesters
promoted
by
readily
accessible
chiral
copper
catalyst
involving
an
easy-to-prepare
isolable
organoborate
reagent.
Reactions
reach
completion
just
few
minutes
at
room
temperature.
importance
this
advance
highlighted
the
preparation
intermediates
previously
generate
racemic
PPAPs.
We
also
nemorosonol
(14
steps,
20%
yield)
its
one-step
conversion
another
PPAP,
garcibracteatone
(52%
yield).
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(38), P. 7025 - 7029
Published: Sept. 14, 2023
A
new
approach
is
proposed
for
the
divergent
and
regioselective
synthesis
of
(E)-2-bromo-1-phenylvinyl
trifluoromethanesulfonates
through
alkyne
difunctionalization
by
employing
a
compatible
system
abundantly
available
alkynes,
N-bromosuccinimide
(NBS),
trimethylsilyl
trifluoromethanesulfonate
(TMSOTf)
catalyzed
ruthenium(III)
acetate
[Ru(OAc)3].
It
novel
method
preparation
vinyl
triflate
it
offers
fundamental
basis
development
advanced
functional
compounds,
including
drugs
organic
materials.
Unlike
previously
reported
methods,
protocol
can
tolerate
broad
range
groups.
Alkynes
derived
from
bioactive
molecules,
such
as
l(−)-borneol,
demonstrate
potential
value
this
reaction
in
synthesis.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(44)
Published: Sept. 26, 2023
Abstract
Asymmetric
Olefin
Metathesis
(AOM)
represents
a
highly
versatile
synthetic
tool
to
lead
relevant
chiral
building
blocks
with
excellent
enantiopurity.
As
the
Z
‐alkene
moiety
is
ubiquitous
in
wide
range
of
natural
products,
development
catalysts
which
are
able
control
both
‐selectivity
and
enantioselectivity
metathesis
transformations
high
demands.
This
review
aims
provide
comprehensive
overview
covering
all
breakthroughs
accomplished
field
challenging
‐enantioselective
olefin
metathesis,
interest
total
synthesis
complex
molecules.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(32), P. 22485 - 22497
Published: July 30, 2024
Stereochemically
defined
organofluorine
compounds
are
central
to
drug
discovery
and
development.
Here,
we
present
a
catalytic
cross-metathesis
method
for
the
synthesis
of
The Journal of Physical Chemistry A,
Journal Year:
2023,
Volume and Issue:
127(45), P. 9465 - 9472
Published: Nov. 2, 2023
Stereoselective
control
of
the
cross
metathesis
olefins
is
a
crucial
aspect
synthetic
procedures.
In
this
study,
we
utilized
density
functional
theory
methods
to
calculate
thermodynamic
and
kinetic
descriptors
explore
stereoselectivity
between
allylbenzene
2-butene-1,4-diyl
diacetate.
A
ruthenium-based
complex,
characterized
primarily
by
an
anthracene-9-thiolate
ligand,
was
designed
in
silico
completely
restrict
E
conformation
through
bottom-bound
mechanism.
Our
investigation
kinetics
all
feasible
propagation
routes
demonstrated
that
Z-stereoisomers
products
can
be
synthesized
with
energy
cost
only
13
kcal/mol.
As
result,
encourage
further
research
into
strategies
outlined
work.
