Synthesis,
Journal Year:
2023,
Volume and Issue:
55(22), P. 3799 - 3808
Published: Aug. 2, 2023
Abstract
gem-Diborylalkanes
have
recently
emerged
as
valuable
synthons
for
diverse
C–C
bond-forming
reactions.
They
represent
an
important
class
of
bifunctional
reagents
that
can
be
applied
the
synthesis
simple
to
complex
skeletons.
Herein,
we
report
a
Pd-catalysed
hydrogenation
method
gem-diborylalkanes
from
corresponding
gem-diborylalkenes,
which
are
themselves
prepared
aldehydes
and
ketones
using
known
procedures.
In
addition,
transformations
two
representative
gem-diborylalkane
products
discussed
leading
range
functionalised
derivatives.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3822 - 3827
Published: April 26, 2024
Lithiated
1,1-diborylalkanes
have
been
used
as
nucleophilic
coupling
partners
with
a
range
of
oxygen-based
electrophiles,
including
esters,
carbonyls,
and
epoxides.
However,
their
reactivity
nitrogen-based
such
aziridines,
has
remained
relatively
understudied.
Herein,
we
show
that
lithiated
react
α-halo
α-tosyl
aziridines
to
yield
borylated
(aminomethyl)cyclopropanes–a
privileged
scaffold
within
medicinal
chemistry.
The
reaction
displays
high
levels
diastereoselectivity,
enabling
careful
control
up
three
stereocenters
single
transformation.
DFT
studies
provide
insight
into
the
mechanism,
which
diverges
from
observed
analogous
epihalohydrin
starting
materials.
Derivatization
were
also
performed
on
products
demonstrate
utility
boron
amine
handles.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 3, 2025
The
carbanion
derived
from
chlorodiborylmethane
can
act
as
a
soft
nucleophile,
while
the
halogen
substituent
subsequently
function
leaving
group.
Taking
advantage
of
this
feature,
we
herein
have
developed
an
efficient
synthesis
gem-diborylcyclopropyl
ketones
diverse
range
enone
substrates.
We
also
demonstrated
synthetic
utility
protocol
by
leveraging
highly
transformable
nature
cyclopropyl
moiety
and
C-B
bonds.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 22, 2024
α-Halogenated
geminal
bis(boronates)
are
emerging
as
multifunctional
building
blocks
for
organic
synthesis.
Currently,
their
synthetic
utilization
is
still
restricted
due
to
a
lack
of
efficient
preparation
methods.
Herein,
we
report
direct,
modular
synthesis
gem-iododiborylalkanes
using
alkyl
halides
and
lithiated
chlorodiborylmethane
reagent.
Compared
with
previously
reported
methods,
this
protocol
features
assembly,
high
efficiency,
good
tolerance
various
functional
groups.
Organometallics,
Journal Year:
2023,
Volume and Issue:
42(18), P. 2644 - 2650
Published: April 17, 2023
A
convenient
one-pot
synthesis
of
(tBu3P)2Pd(0)
was
successfully
carried
out
by
using
various
air-stable
Pd(II)
salts,
such
as
Pd(cod)Cl2,
Pd(nbd)Cl2,
Pd(CH3CN)2Cl2,
or
Pd(PhCN)2Cl2,
without
the
use
an
external
reducing
agent.
Using
Pd(cod)Cl2
precursor,
large-scale
accomplished
in
excellent
yield
and
purity.
Another
protocol
also
developed
for
L2Pd(0)
complexes
via
atom
economical
method
reacting
situ
generated
LPd(R-allyl)Cl
(L
=
tBu3P,
Cy3P,
(o-Tol)3P,
CataXCium
A,
AmPhos,
QPhos:
R
H,
Me,
Ph)
with
1
equivalent
L
presence
a
base
yields
ranging
from
74%
to
92%,
although
process
can
be
further
optimized.
These
methods
are
superior
those
reported
literature.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(29), P. 16186 - 16192
Published: June 24, 2023
A
carbene
bearing
two
geminal
boryl
substituents,
called
diborylcarbene
(DBC),
has
been
predicted
to
be
highly
Lewis
acidic
in
sharp
contrast
the
well-studied
persistent
carbenes
stabilized
by
π-donating
substituents.
Studies
on
DBC
have
limited
either
base-trapping
or
theoretical
calculations.
Herein,
we
developed
chemical
equivalents
for
DBC,
namely,
K/X-diborylcarbenoids
2X
(X
=
F
Cl).
Treatment
of
2F
with
Al(C6F5)3
yielded
[AlF(C6F5)3]--stabilized
1-FAl,
which
showed
a
significant
low-field
shift
carbenoid
carbon
from
169
ppm
(doublet,
coupling
19F)
242
(singlet).
The
loss
halogen
was
also
detected
through
electrospray
ionization
time-of-flight
mass
spectrometry
analysis
only
presence
Al(C6F5)3.
Generated
1
1-FAl
2Cl
successfully
trapped
excess
amounts
trialkylphosphines
(PR3,
R
Me
Et),
afforded
corresponding
DBC-PR3
adducts.
In
addition,
acidity
evaluated
both
experimentally
and
theoretically
reveal
that
is
one
most
species
among
neutral
molecules.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(14)
Published: Feb. 1, 2023
Abstract
This
report
describes
the
unprecedented
electrooxidation
of
a
solvent
(e.g.,
DMF)‐ligated
B
2
cat
complex,
whereby
solvent‐stabilized
boryl
radical
is
formed
via
quasi‐homolytic
cleavage
B−B
bond
in
DMF‐ligated
cation.
Cyclic
voltammetry
and
density
functional
theory
provide
evidence
to
support
this
novel
activation
strategy.
Furthermore,
strategy
for
electrochemical
gem
‐diborylation
‐bromides
paired
electrolysis
developed
first
time,
affording
range
versatile
‐diborylalkanes,
which
are
widely
used
synthetic
society.
Notably,
reaction
approach
scalable,
transition‐metal‐free,
requires
no
external
activator.
