Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
136(4)
Published: Dec. 8, 2023
Abstract
General
methods
for
the
preparation
of
geminal
bis(boronates)
are
great
interest
due
to
their
widespread
applications
in
organic
synthesis.
While
terminal
gem
‐diboron
compounds
readily
accessible,
construction
sterically
encumbered,
internal
analogues
has
remained
a
prominent
challenge.
Herein,
we
report
formal
umpolung
strategy
access
these
valuable
building
blocks.
The
available
1,1‐diborylalkanes
were
first
converted
into
corresponding
α‐halogenated
derivatives,
which
then
serve
as
electrophilic
components,
undergoing
substitution
with
diverse
array
nucleophiles
form
series
C−C,
C−O,
C−S,
and
C−N
bonds.
This
protocol
features
good
tolerance
steric
hindrance
wide
variety
functional
groups
heterocycles.
Notably,
this
can
also
be
extended
synthesis
diaryl
compounds,
therefore
providing
general
approach
various
types
bis(boronates).
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(3)
Published: Dec. 8, 2023
Abstract
The
development
of
boron
reagents
is
crucial
for
synthetic
chemistry.
Herein,
we
present
a
scalable
and
practical
synthesis
diborodichloromethane
(DBDCM)
through
the
reaction
trichloromethyllithium
with
bis(pinacolato)diboron
(B
2
pin
).
resulting
DBDCM
reagent
serves
as
basic
unit
construction
various
structurally
diverse
gem
‐diborylalkanes
controllable
C−Cl
functionalizations.
Moreover,
have
developed
consecutive
tetra‐functionalizations
tertiary
quaternary
carbon
containing
molecules.
use
isotopically
enriched
13
C‐chloroform
10
B
enables
C‐DBDCM
B‐DBDCM
reagents,
which
are
beneficial
convenient
carbon‐13
boron‐10
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(18)
Published: March 6, 2024
Geminal
bis(boronates)
are
versatile
synthetic
building
blocks
in
organic
chemistry.
The
fact
that
they
predominantly
serve
as
nucleophiles
the
previous
reports,
however,
has
restrained
their
potential.
Herein
we
disclose
ambiphilic
reactivity
of
α-halogenated
geminal
bis(boronates),
which
first
catalytic
utilization
was
accomplished
by
merging
a
formal
Heck
cross-coupling
with
highly
diastereoselective
allylboration
aldehydes
or
imines,
providing
new
avenue
for
rapid
assembly
polyfunctionalized
boron-containing
compounds.
We
demonstrated
this
cascade
reaction
is
efficient
and
compatible
various
functional
groups,
wide
range
heterocycles.
In
contrast
to
classical
Pd(0/II)
scenario,
mechanistic
experiments
DFT
calculations
have
provided
strong
evidence
cycle
involving
Pd(I)/diboryl
carbon
radical
intermediates.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 20, 2024
Abstract
The
stereoselective
cyclopropanation
of
olefins
with
“boron
ylide”
is
disclosed
for
the
first
time,
providing
a
modular
strategy
synthesis
stereospecific
diboryl‐functionalized
cyclopropanes.
chiral
gem
‐diborylcyclopropanes
are
synthesized
excellent
enantioselectivity
aid
auxiliary.
Based
on
powerful
transformable
ability
boryl
group,
those
challenging
multi‐quaternary
carbon
centers
in
cyclopropane
units
have
been
facilely
constructed
stereoselectivity.
Control
experiments
indicate
that
groups
necessary
both
chemoselectivity
and
stereoselectivity
control.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(4)
Published: Dec. 8, 2023
Abstract
General
methods
for
the
preparation
of
geminal
bis(boronates)
are
great
interest
due
to
their
widespread
applications
in
organic
synthesis.
While
terminal
gem
‐diboron
compounds
readily
accessible,
construction
sterically
encumbered,
internal
analogues
has
remained
a
prominent
challenge.
Herein,
we
report
formal
umpolung
strategy
access
these
valuable
building
blocks.
The
available
1,1‐diborylalkanes
were
first
converted
into
corresponding
α‐halogenated
derivatives,
which
then
serve
as
electrophilic
components,
undergoing
substitution
with
diverse
array
nucleophiles
form
series
C−C,
C−O,
C−S,
and
C−N
bonds.
This
protocol
features
good
tolerance
steric
hindrance
wide
variety
functional
groups
heterocycles.
Notably,
this
can
also
be
extended
synthesis
diaryl
compounds,
therefore
providing
general
approach
various
types
bis(boronates).
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 25, 2025
A
modular
synthesis
method
for
1,4-diketones
has
been
developed.
Utilizing
inexpensive
carboxylic
acid
esters
as
carbonyl
sources
and
tetraborylethane
(TBE)
a
nucleophilic
reagent,
one-pot
strategy
constructing
two
C-C
bonds
was
established.
Notably,
this
reaction
proceeds
without
the
involvement
of
transition
metals
exhibits
excellent
functional
group
compatibility.
diverse
array
α-substituted
were
synthesized
using
various
electrophiles
capture.
RSC Advances,
Journal Year:
2025,
Volume and Issue:
15(13), P. 10265 - 10272
Published: Jan. 1, 2025
This
study
introduces
an
efficacious
palladium-catalyzed
method
for
the
regioselective
and
stereoselective
cross-coupling
of
gem
-difluorinated
cyclopropanes
with
array
-diborylalkanes
under
mild
reaction
conditions.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 1, 2025
Herein,
we
report
a
nickel-catalyzed
1,1-carboboration
of
di-
and
trisubstituted
alkenyl
boronates
through
chain-walking
strategy.
This
reaction
effectively
addresses
the
polarity-mismatch
problem
via
ligand
control,
enabling
coupling
various
carbon-based
electrophiles
while
accommodating
broad
range
functional
groups.
The
approach
yields
diverse
tetrasubstituted
carbon
gem-diboronate
derivatives
with
exceptional
regioselectivity.
synthetic
utility
this
method
is
further
demonstrated
concise
synthesis
high-value
bioactive
molecules.
