Angewandte Chemie,
Год журнала:
2023,
Номер
136(4)
Опубликована: Дек. 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,
Год журнала:
2023,
Номер
62(38)
Опубликована: Авг. 2, 2023
Cyclopropane
skeletons
play
a
prominent
role
in
the
development
of
organic
synthesis
and
pharmaceutical
chemistry.
Herein,
we
report
design
stable,
multifunctional
(diborylmethyl)iodide
reagent
(CHI(Bpin)2
)
for
photoinduced
cyclopropanation
alkenes,
providing
an
array
1,2-substituted
cyclopropylboronates
good
yields.
This
α-haloboronic
ester
can
be
readily
synthesized
on
multigram
scale
from
commercially
available
starting
materials.
Furthermore,
protocol
displays
high
chemo-
diastereoselectivity,
excellent
functional-group
tolerance,
allows
late-stage
borylcyclopropanation
complex
molecules.
Mechanistic
studies
reveal
that
proceeds
through
radical
addition/polar
cyclization
pathway
mediated
by
photocatalyst
fac-Ir(ppy)3
visible
light.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Дек. 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,
Год журнала:
2024,
Номер
63(18)
Опубликована: Март 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,
Год журнала:
2023,
Номер
63(4)
Опубликована: Дек. 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,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 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.
The Chemical Record,
Год журнала:
2024,
Номер
24(3)
Опубликована: Фев. 2, 2024
Abstract
The
wide
applications
of
alpha‐boryl
carbanions
in
selective
coupling
with
organohalides,
imines/carbonyls
and
conjugated
unsaturated
substrates
has
become
an
interesting
tool
for
organic
synthesis.
Strategically,
the
inclusion
heteroatoms,
such
as
Si,
S,
N,
F,
Cl,
Br
I
alpha
position
opens
a
new
venue
towards
multifunctionalities
molecular
design.
Here,
conceptual
practical
view
on
powerful
carbanions,
containing
α‐silicoboron,
α‐thioboron,
α‐haloboron
α‐aminoboron
is
given,
well
prespective
their
efficient
application
electrophilic
trapping.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 23, 2025
Comprehensive
Summary
Allenylboronates
are
valuable
synthetic
building
blocks
and
have
garnered
significant
interest.
However,
their
1,3‐diboyl
substituted
analogs
not
been
reported.
Herein,
we
disclosed
a
novel
method
for
creating
allenes
from
gem
‐iododiboron
compounds
alkynyl
Grignard
reagents.
The
starting
materials
initially
converted
into
the
corresponding
propargylic
‐bis(boronates),
which
then
undergo
an
intermolecular
boryl
group
transfer
to
afford
allenes,
as
confirmed
by
mechanistic
studies.
This
features
good
tolerance
steric
hindrance
is
compatible
with
wide
variety
of
functional
groups.
α-halo
alkylboronic
esters,
acting
as
ambiphilic
synthons,
play
a
pivotal
role
versatile
intermediates
in
fields
like
pharmaceutical
science
and
organic
chemistry.
The
sequential
transformation
of
carbon-boron
carbon-halogen
bonds
into
broad
range
carbon-X
allows
for
programmable
bond
formation,
facilitating
the
incorporation
multiple
substituents
at
single
position
streamlining
synthesis
complex
molecules.
Nevertheless,
synthetic
potential
these
compounds
is
constrained
by
limited
reaction
patterns.
Additionally,
conventional
methods
often
necessitate
use
bulk
toxic
solvents,
exhibit
sensitivity
to
air/moisture,
rely
on
expensive
metal
catalysts,
involve
extended
times.
In
this
report,
ball
milling
technique
introduced
that
overcomes
limitations,
enabling
external
catalyst-free
multicomponent
coupling
aryl
diazonium
salts,
alkenes,
simple
halides.
This
approach
offers
general
straightforward
method
obtaining
diverse
array
thereby
paving
way
extensive
utilization
synthons
fine
chemicals.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(33)
Опубликована: Май 31, 2024
Abstract
gem
‐Diborylalkanes
are
highly
valuable
building
blocks
in
organic
synthesis
and
pharmaceutical
chemistry
due
to
their
ability
participate
multi‐step
cross‐coupling
transformations,
allowing
for
the
rapid
generation
of
molecular
complexity.
While
progress
has
been
made
synthetic
metholodology,
construction
β‐tertiary
C(sp
3
)‐rich
‐diborylalkanes
remains
a
challenge
substrate
limitations
steric
hindrance
issues.
An
approach
is
presented
that
utilizes
synergistic
photoredox
copper
catalysis
achieve
efficient
)−C(sp
)
alkyl
N
‐hydroxyphthalimide
esters,
which
can
easily
be
obtained
from
carboxylic
acids,
with
diborylmethyl
species,
providing
series
1°,
2°,
even
3°
β
positions.
Furthermore,
this
also
applied
complex
medicinal
compounds
natural
products,
offering
access
complexity
late‐stage
functionalization
drug
candidates.
Mechanistic
experiments
revealed
Cu(I)
species
participated
both
process
key
bond‐forming
step.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(19), С. 14246 - 14254
Опубликована: Сен. 21, 2023
α-Halogenated
boronic
esters
are
versatile
building
blocks
that
can
be
diversified
into
a
wide
variety
of
polyfunctionalized
molecules.
However,
their
synthetic
potential
has
been
hampered
by
limited
preparation
methods.
Herein,
we
report
visible
light-induced
C-H
bromination
reaction
readily
available
benzyl
esters.
This
method
features
high
yields,
mild
conditions,
simple
operation,
and
good
functional
group
tolerance.
The
analogous
chlorides
iodides
accessed
via
Finkelstein
reaction.
Synthesis
halogenated
geminal
diborons
also
demonstrated.
