Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(16), С. 1860 - 1866
Опубликована: Апрель 18, 2024
Comprehensive
Summary
By
rational
modification
of
electronic
and
steric
properties
pincer
ligands,
a
Co/Fe
dual
catalyst
system
is
developed
for
one‐pot
sequential
Markovnikov
alkyne
hydrosilylation
stereoselective
alkene
isomerization.
The
protocol
provides
an
atom‐economical
efficient
approach
to
trisubstituted
(
E
)‐alkenyl
silanes
from
widely
accessible
terminal
alkynes
with
high
regio‐
stereoselectivities
under
mild
conditions.
utility
this
reaction
was
demonstrated
by
gram‐scale
synthesis
derivatization
bioactive
molecules.
radical
clock
trapping
experiments
indicated
that
pathway
might
be
operative
in
the
isomerization
step.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5366 - 5374
Опубликована: Фев. 14, 2024
Two
enantioselective
approaches
to
synthesize
chiral
skipped
diboronate
compounds
have
been
developed,
relying
on
copper-catalyzed
one-pot
asymmetric
ring-opening
diboration
of
arylidenecyclopropanes.
A
wide
range
arylidenecyclopropanes
react
smoothly
with
HBpin
in
the
presence
CuOAc
and
(R)-DTBM-Segphos,
affording
1,4-diboronates
high
enantioselectivity
(up
99%
ee).
Meanwhile,
a
variety
selectively
B2pin2
(S,S)-Ph-BPE
sequential
addition
MeOH,
providing
1,3-diboronates
98%
These
enantioenriched
1,3-
can
undergo
various
enantiospecific
transformations
minimal
loss
their
enantiopurity.
Mechanistic
studies
reveal
that
these
two
processes
start
CuH-catalyzed
hydroboration
form
mixture
Z/E-homoallyl
boronate
intermediates,
which
subsequently
second
or
Cu-Bpin-catalyzed
protoboration
produce
1,3-diboronates,
respectively.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 7, 2023
Ligand-controlled
regiodivergent
cobalt-catalyzed
ring-opening
dihydroboration
of
arylidenecyclopropanes
is
developed
to
access
synthetically
versatile
skipped
diboronates
with
catalysts
generated
in
situ
from
Co(acac)2
and
dpephos
or
xantphos.
A
variety
reacted
pinacolborane
(HBpin)
form
the
corresponding
1,3-
1,4-diboronates
high
isolated
yields
regioselectivity.
Skipped
diboronate
products
these
reactions
can
undergo
various
transformations
allow
selective
installation
two
different
functional
groups
along
alkyl
chains.
Mechanistic
studies
suggest
that
combine
hydroboration
homoallylic
allylic
boronate
intermediates.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(29), С. 13071 - 13078
Опубликована: Июль 13, 2022
Despite
the
frequent
occurrence
of
γ-branched
amines
in
bioactive
molecules,
direct
catalytic
asymmetric
synthesis
this
structural
motif
containing
a
remote
stereocenter
remains
an
important
synthetic
challenge.
Here,
we
report
amide-directed,
rhodium-catalyzed
highly
diastereo-
and
enantioselective
hydroboration
unactivated
internal
alkenes.
This
method
provided
facile
access
to
enantioenriched
β,γ-vicinal
stereocenters.
The
application
strategy
molecules
was
demonstrated.
Computational
studies
indicated
that
migratory
insertion
alkene
into
rhodium
hydride
controls
enantioselectivity.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(6), С. 768 - 819
Опубликована: Янв. 17, 2023
This
review
updates
the
field
of
enantioselective
domino
reactions
promoted
by
chiral
catalysts
derived
from
first
row
metals,
such
as
zinc,
iron,
copper,
scandium,
nickel,
cobalt,
titanium,
chromium
and
magnesium
special
case,
published
since
beginning
2019.
It
illustrates
how
much
a
diversity
these
allow
an
impressive
range
novel
highly
many
types
to
be
achieved,
providing
one-pot
access
very
complex
functionalized
molecules
simple
starting
materials.
Inorganic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(12), С. 3656 - 3663
Опубликована: Янв. 1, 2023
Pincer
cobalt
complexes
based
on
a
triazine
backbone
have
been
used
as
efficient
catalysts
for
the
hydroboration
reaction
of
alkenes.
The
presented
protocol
shows
unique
selectivity
distinguishing
vinylsilyl
from
another
alkenyl
or
alkynyl
groups.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(19)
Опубликована: Янв. 11, 2024
Abstract
Vinylcyclopropanes
(VCPs)
are
important
building
blocks
with
multifaceted
reactivity.
Catalytic
asymmetric
ring
opening
of
vinylcyclopropanes
is
a
highly
efficient
process
to
access
valuable
chiral
molecules
diverse
functionalities
that
can
be
further
functionalized
for
series
synthetic
purposes.
VCPs
very
well‐known
substrates
cycloaddition
reactions
and
this
chemistry
has
been
widely
explored.
On
the
contrary,
despite
enormous
potential,
development
new
innovative
strategies
catalytic,
somewhat
underdeveloped.
Recently,
several
significant
examples
have
emerged
in
literature
various
both
activated
unactivated
involve
transition
metal
catalysis.
These
developments
relevant
additions
vinylcyclopropane
chemistry.
In
review,
we
aim
summarize
all
catalytic
transformations
reported
till
date
provide
comprehensive
analysis
these
research
outcomes.
Chemical Science,
Год журнала:
2022,
Номер
13(36), С. 10743 - 10751
Опубликована: Янв. 1, 2022
We
succeeded
in
synthesizing
five
different
types
of
multiply
arylated
alkanes
from
diarylketones
a
single
step.
The
key
for
this
method
is
the
generation
diarylphosphinates
via
phospha-Brook
rearrangement
ketones
with
phosphine
oxide.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(7), С. 4569 - 4580
Опубликована: Март 21, 2023
Organoboron
showed
great
potential
in
the
synthesis
of
various
high-value
chemical
compounds.
Direct
hydroboration
olefins
has
been
witnessed
over
time
as
a
mainstream
method
for
organoboron
In
this
work,
an
electroreductive
anti-Markovnikov
approach
with
readily
available
B2pin2
to
synthesize
valuable
compounds
high
chemo-
and
regioselectivities
under
metal
catalyst-free
conditions
was
reported.
This
protocol
exhibited
broad
substrate
scope
good
functional-group
tolerance
on
styrenes
heteroaromatic
olefins,
providing
synthetically
useful
alkylborons
efficiency
even
deuterium
borylation
products
D-incorporation
when
CD3CN
employed
solvent.
Furthermore,
gram-scale
reactions
extensive
functional
derivatization
further
highlighted
method.
