Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 24, 2023
Herein
we
reported
a
transition
metal-free
deborylative
cyclization
strategy,
based
on
which
two
routes
have
been
developed,
generating
racemic
and
enantioenriched
cyclopropylboronates.
The
of
geminal-bis(boronates)
bearing
leaving
group
was
highly
diastereoselective,
tolerating
few
functional
groups
applicable
to
heterocycles.
When
optically
active
epoxides
were
used
as
the
starting
materials,
cyclopropylboronates
could
be
efficiently
prepared
with
>99
%
stereospecificity.
Mechanistic
studies
showed
that
at
γ-position
played
crucial
role
significantly
promoted
activation
gem-diboron
moiety.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(6), С. 2796 - 2821
Опубликована: Март 23, 2020
The
iridium-catalysed
borylation
of
aromatic
C−H
bonds
has
become
the
preferred
method
for
synthesis
organoboron
compounds.
reaction
is
highly
efficient,
tolerant
a
broad
range
substituents
and
can
be
applied
to
both
carbocyclic
heterocyclic
substrates.
regioselectivity
activation
dominated
by
steric
considerations
there
have
been
considerable
efforts
develop
more
selective
processes
less
constrained
However,
most
these
focused
on
benzenoid-type
substrates
in
contrast,
heteroarenes
remain
much
desired
but
challenging
with
position
and/or
nature
heteroatom(s)
significantly
affecting
reactivity
regioselectivity.
This
review
will
survey
heteroarenes,
focusing
influence
electronic
effects
regiochemical
outcome
and,
linking
current
mechanistic
understandings,
provide
insights
what
currently
possible
where
further
developments
are
required.
Science,
Год журнала:
2021,
Номер
372(6538), С. 175 - 182
Опубликована: Апрель 9, 2021
Slipping
boron
into
alkyl
ethers
The
carbon–oxygen
bonds
that
hold
together
are
relatively
inert.
Lyu
et
al.
report
zinc
and
nickel
can
team
up
to
insert
between
the
carbon
oxygen
using
an
unusual
mechanism.
First,
a
dibromoborane
pries
open
bond
with
help
from
ion.
Next,
stitches
boron,
oxidation
of
metallic
starts
cycle
over
again.
Versatile
reactivity
at
inserted
center
then
add
carbons
original
ether
or
swap
out
for
nitrogen.
Science
,
this
issue
p.
175
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16508 - 16516
Опубликована: Июль 20, 2023
Enantioenriched
organoboron
intermediates
are
important
building
blocks
in
organic
synthesis
and
drug
discovery.
Recently,
transition
metal-catalyzed
enantioselective
1,2-metalate
rearrangements
of
alkenylboronates
have
emerged
as
an
attractive
protocol
to
access
these
valuable
reagents
by
installing
two
different
carbon
fragments
across
C═C
π-bonds.
Herein,
we
report
the
development
iridium-catalyzed
asymmetric
allylation-induced
rearrangement
bicyclo[1.1.0]butyl
(BCB)
boronate
complexes
enabled
strain
release,
which
allows
difunctionalization
C-C
σ-bonds,
including
dicarbonation
carboboration.
This
provides
a
variety
enantioenriched
three-dimensional
1,1,3-trisubstituted
cyclobutane
products
bearing
boronic
ester
that
can
be
readily
derivatized.
Notably,
reaction
gives
trans
diastereoisomers
result
from
anti-addition
σ-bond,
is
contrast
syn-additions
observed
for
reactions
promoted
PdII-aryl
other
electrophiles
our
previous
works.
The
diastereoselectivity
has
been
rationalized
based
on
combination
experimental
data
density
functional
theory
calculations,
suggest
BCB
highly
nucleophilic
react
via
early
states
with
low
activation
barriers.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(6), С. 4026 - 4035
Опубликована: Фев. 1, 2024
Herein,
we
report
a
divergent
synthesis
of
fluoroalkyl
ketones
through
visible-light-induced
reactions
between
readily
available
organoboronic
esters
and
acylsilanes.
Selective
control
the
reactivity
in
situ
generated
organoboronate
complexes
is
key
to
achieving
transformations.
Under
basic
conditions,
undergo
deboronative
fluoride
elimination,
resulting
formation
enol
silyl
ethers
as
intermediates
that
react
with
various
electrophiles
generate
defluorinated
products.
Moreover,
combination
peroxide,
1,2-shift
group
favored
over
elimination
ketal
intermediates,
leading
This
transition-metal-free
reaction
operationally
simple,
aryl,
alkenyl,
alkyl
boronic
are
all
suitable
substrates.
The
synthetic
potential
has
been
demonstrated
by
gram-scale
facile
bioactive
molecules
including
zifrosilone
its
analogs.
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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 16295 - 16305
Опубликована: Май 30, 2024
Atomically
precise
metal
nanoclusters
(NCs)
have
become
an
important
class
of
catalysts
due
to
their
catalytic
activity,
high
surface
area,
and
tailored
active
sites.
However,
the
design
development
bond-forming
reaction
based
on
copper
NCs
are
still
in
early
stages.
Herein,
we
report
synthesis
atomically
nanocluster
with
a
planar
core
unique
shell,
[Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+
(Cu45)
(TBBT:
4-tert-butylbenzenethiol;
TPP:
triphenylphosphine),
yield
via
one-pot
reduction
method.
The
resulting
structurally
well-defined
Cu45
is
highly
efficient
catalyst
for
hydroboration
alkynes
alkenes.
Mechanistic
studies
show
that
single-electron
oxidation
situ-formed
ate
complex
enables
formation
boryl-centered
radicals
under
mild
conditions.
This
work
demonstrates
promise
as
C–B
heteroatom
reactions.
compatible
wide
range
alkenes
functional
groups
producing
hydroborated
products.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 16, 2025
Quaternary
carbon
centers
are
widespread
structural
motifs,
thus
representing
extensive
interest
in
organic
synthesis.
We
describe
here
an
efficient
nickel-catalyzed
intermolecular,
Markovnikov-selective
arylation
of
minimally
functionalized
alkenes
with
stable
organoborons,
affording
a
broad
range
cyclic
or
acyclic
quaternary
under
mild
conditions.
The
utilization
the
diimine
ligand
is
critical
for
high
reactivity
and
chemoselectivity.
Furthermore,
using
bulky
chiral
as
Ni
catalyst,
stereocenters
can
be
readily
prepared
levels
enantiocontrol.
Mechanism
studies
suggest
that,
before
protonation,
rare
nickel
shift
from
alkyl
to
aryl
might
occur.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(11), С. 4370 - 4374
Опубликована: Янв. 7, 2020
A
modular,
site-selective
1,2-dicarbofunctionalization
of
vinyl
boronates
with
organic
halides
through
dual
catalysis
is
described.
This
reaction
proceeds
under
mild
conditions
and
characterized
by
excellent
chemo-
regioselectivity.
It
thus
represents
a
complementary
new
technique
for
preparing
densely
functionalized
alkyl
boron
architectures
from
simple
accessible
precursors.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(39), С. 16859 - 16872
Опубликована: Июнь 27, 2020
The
stereospecific
1,2-migration
of
boronate
complexes
is
one
the
most
representative
reactions
in
boron
chemistry.
This
process
has
been
used
extensively
to
develop
powerful
methods
for
asymmetric
synthesis,
with
applications
spanning
from
pharmaceuticals
natural
products.
Typically,
driven
by
displacement
an
α-leaving
group,
oxidation
α-boryl
radical,
or
electrophilic
activation
alkenyl
complex.
aim
this
article
summarize
recent
advances
rapidly
expanding
field
electrophile-induced
groups
sp
