Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(34)
Published: June 16, 2023
Abstract
Operationally
simple
strategies
to
assemble
boron
containing
organic
frameworks
are
highly
enabling
in
synthesis.
While
conventional
retrosynthetic
logic
has
engendered
many
platforms
focusing
on
the
direct
formation
of
C−B
bonds,
α‐boryl
radicals
have
recently
reemerged
as
versatile
open‐shell
alternatives
access
organoborons
via
adjacent
C−C
bond
formation.
Direct
light‐enabled
α‐activation
is
currently
contingent
photo‐
or
transition
metal‐catalysis
activation
efficiently
generate
radical
species.
Here,
we
disclose
a
facile
α‐halo
boronic
esters
using
only
visible
light
and
Lewis
base
enable
homolytic
scission.
Intermolecular
addition
styrenes
facilitates
rapid
construction
E
‐allylic
esters.
The
simplicity
permits
strategic
merger
this
construct
with
selective
energy
transfer
catalysis
complimentary
stereodivergent
synthesis
Z
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(3)
Published: Oct. 12, 2022
A
new
method
to
access
β-keto-gem-diborylalkanes,
by
direct
deoxygenative
radical
addition
of
aromatic
carboxylic
acids
gem-dibortlalkenes,
is
described.
The
reaction
proceeds
under
mild
photoredox
catalysis
and
involves
the
photochemical
C-O
bond
activation
in
presence
PPh
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Sept. 28, 2022
Copper-catalyzed
regioselective
quadruple
borylation
of
terminal
alkynes
has
been
developed
employing
a
copper
catalyst
generated
from
CuI
and
dcpe
(1,2-bis(dicyclohexylphosphino)ethane).
A
wide
range
undergo
this
multi-borylation
reaction
to
afford
the
corresponding
1,1,2,2-tetraborylalkanes
in
high
yields.
Mechanistic
studies
reveal
that
proceeds
through
copper-catalyzed
sequential
double
1,2-diborylation
1,2-diborylalkene
intermediates.
This
protocol
represents
most
straightforward
atom-economic
approach
prepare
sp3
-tetra-organometallic
reagents
readily
accessible
with
commercially
available
catalysts.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 11, 2025
Herein,
we
disclose
a
manganese-catalyzed
approach
that
enables
the
direct
iododiborylcarbofunctionalization
of
alkynes
with
(diboronmethyl)iodide
under
mild
conditions.
This
grants
access
to
range
structurally
unique
and
synthetically
useful
γ-iodine-substituted
gem-bis(boronate)s,
which
have
hitherto
been
inaccessible.
atom-economical
strategy
displays
excellent
functional-group
tolerance,
encompasses
wide
applicable
substrates,
demonstrates
high
Z:E
selectivity
(up
96:4).
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(15)
Published: March 5, 2023
Abstract
A
novel
and
easy‐to‐execute
light‐driven
protocol
for
the
preparation
of
alkyl
boronic
acid
pinacol
esters
from
vinyl
boronate
using
N
‐hydroxyphthalimide
as
potential
precursor
is
described.
In
this
photochemical
protocol,
ester's
fragmentation
generates
C‐centered
radicals,
which
undergo
a
radical
Michael
addition
to
ester
furnishing
desired
products.
good
substrate
scope
having
various
functionalities
presented
high
yields
are
obtained.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
30(2)
Published: Oct. 4, 2023
Abstract
Carbon‐centered
radicals
stabilized
by
adjacent
boron
atoms
are
underexplored
reaction
intermediates
in
organic
synthesis.
This
study
reports
the
development
of
vinyl
cyclopropyl
diborons
(VCPDBs)
as
a
versatile
source
previously
unknown
homoallylic
α,α‐diboryl
via
thiyl
radical
catalyzed
diboron‐directed
ring
opening.
These
diboryl
underwent
smooth
[3+2]
cycloaddition
with
variety
olefins
to
provide
cyclopentanes
good
excellent
diastereoselectivity.
In
contrast
trans
‐diastereoselectivity
observed
most
dicarbonyl
activated
VCPs,
VCPDBs
showed
remarkable
preference
for
formation
cis
‐cyclopentane
diastereomer
which
was
confirmed
quantitative
NOE
and
2D
NOESY
studies.
The
‐stereochemistry
cyclopentane
products
enabled
concise
intramolecular
Heck
approach
rare
tricyclic
cyclopentanoid
framework
containing
diboron
group.
mild
conditions
also
allowed
one‐pot
VCP
ring‐opening,
cycloaddition‐oxidation
sequence
afford
disubstituted
cyclopentanones.
Control
experiments
DFT
analysis
mechanism
support
mediated
pathway
rationale
To
authors’
knowledge,
these
first
examples
use
geminal
group
an
activator
opening
α‐boryl
radicals.
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.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(72)
Published: Sept. 26, 2022
We
report
a
designed
stereodivergent
strategy
for
the
synthesis
of
gem-diborylcyclopropanes.
The
reaction
provides
highly
modular
approach
to
prepare
cyclopropane
ring
variants
bearing
gem-(Bpin,Bpin),
gem-(Bpin,Bdan),
and
gem-(Bpin,BF3
K),
with
outstanding
levels
stereocontrol.
This
was
achieved
by
diastereoselective
Pd-catalyzed
cyclopropanation
reactions
gem-diborylalkenes
α-diazoarylacetates
α-diazoaryl-trifluoromethyl.
key
success
this
general
protocol
trifluorination
gem-diborylcyclopropanes,
followed
stereospecific
interconversion
trifluoroborate
salts
into
Bdan
group.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(6), P. 1366 - 1374
Published: Jan. 16, 2024
Abstract
An
atom
transfer
radical
[3+2]
annulation
(ATRAn)
reaction
involving
alkenyl
boronic
esters
and
homoallylic
iodides
provides
a
rapid
access
to
polysubstituted
borylated
cyclopentanes.
A
variety
of
α‐substituted
vinylboronic
are
suitable
substrates
offer
unique
opportunities
for
further
modification
the
formed
5‐membered
ring.
For
instance,
oxidation
ester
an
alcohol
allows
preparation
products
that
corresponds
enol
form
acetone.
Substitution
iodide
by
nucleophile
such
as
lithium
methoxide
without
modifying
moiety
is
also
feasible.
Finally,
using
(3‐acetoxyprop‐1‐en‐2‐yl)boronic
ester,
facile
1,2‐elimination
provided
methylenecyclopentane.
In
this
case,
alkenylboronate
trap
acts
equivalent
allene,
building
block
so
far
elusive
preparative
reactions.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(13), P. 2945 - 2955
Published: April 23, 2024
Abstract
A
formal
atom
transfer
radical
[3+2]
annulation
(ATRAn)
reaction
between
different
homoallyl
precursors
and
1,1‐diborylethene
was
developed.
It
provides
a
rapid
access
to
polysubstituted
cyclopentanes
containing
gem
‐diboronic
ester
moiety.
The
synthetic
utility
of
theses
uniquely
functionalized
5‐membered
rings
is
highlighted
by
their
easy
conversion
attractive
borylated
building
blocks
such
as
1‐borylated
bicyclo[3.1.0]hexanes.
ATRAn
extended
homopropagylic
radicals
giving
unique
allylic
esters
that
could
be
used
in
allylboration
aldehydes.
Furthermore,
this
work
highlights
represents
equivalent
ketene,
so
far
elusive
trap
due
its
daunting
reactivity.
Chemistry - A European Journal,
Journal Year:
2020,
Volume and Issue:
27(7), P. 2294 - 2298
Published: Oct. 16, 2020
Abstract
A
transition‐metal‐free
method
for
the
alkylation
of
gem
‐diborylalkanes
with
α
,β‐unsaturated
ketones
has
been
developed.
It
is
demonstrated
that
α‐boryl
radicals
can
be
generated
efficiently
from
aid
catechol
and
oxidants.
The
formed
through
such
process
engaged
in
conjugate
addition
reaction
α,β‐unsaturated
ketones.
This
transformation
a
straightforward
synthesis
γ
‐borylketones.
