The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(19), P. 14246 - 14254
Published: Sept. 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.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(6), P. 4162 - 4184
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
summary
of
recent
advances
in
nickel-catalyzed
reactions
employing
tertiary
alkyl
electrophiles
for
the
construction
quaternary
carbon
centers.
Science,
Journal Year:
2021,
Volume and Issue:
374(6566), P. 432 - 439
Published: Oct. 22, 2021
Iron
links
a
trio
holds
particular
appeal
as
catalytic
metal—it
is
safe
and
abundant,
well
mainstay
of
enzymatic
reactivity.
Nonetheless,
in
synthetic
construction
carbon-carbon
bonds,
modern
chemists
have
largely
had
to
rely
on
rarer
metals
such
palladium.
Liu
et
al
.
now
report
that
coordination
iron
by
bulky
chelating
phosphine
ligand
enables
efficient
mutual
coupling
three
different
reactants—an
alkyl
halide,
an
aryl
Grignard,
olefin—to
form
two
bonds
(see
the
Perspective
Lefèvre).
A
combination
Mössbauer
spectroscopy,
crystallography,
computational
simulations
illuminates
mechanism.
—JSY
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(36), P. 4346 - 4353
Published: Jan. 1, 2021
This
article
highlights
recent
advances
on
the
base-promoted
deborylative
carbon–carbon
and
carbon–boron
bond-forming
reactions
using
gem-diborylalkanes
as
sources
of
α-borylcabanions.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(38)
Published: June 24, 2022
Recently
the
fruitful
merger
of
organoboron
chemistry
and
photocatalysis
has
come
to
forefront
organic
synthesis,
resulting
in
development
new
technologies
access
complex
(non)borylated
frameworks.
Central
success
this
combination
is
control
boron
hybridisation.
Contingent
on
photoactivation
mode,
as
its
neutral
planar
form
or
tetrahedral
boronate
can
be
used
regulate
reactivity.
This
Minireview
highlights
current
state
art
photocatalytic
processes
utilising
compounds,
paying
particular
attention
role
hybridisation
for
target
transformation.
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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(23), P. 15850 - 15859
Published: May 28, 2024
Light-driven
strategies
that
enable
the
chemoselective
activation
of
a
specific
bond
in
multifunctional
systems
are
comparatively
underexplored
comparison
to
transition-metal-based
technologies,
yet
desirable
when
considering
controlled
exploration
chemical
space.
With
current
drive
discover
next-generation
therapeutics,
reaction
design
enables
strategic
incorporation
an
sp3
carbon
center,
containing
multiple
synthetic
handles
for
subsequent
space
would
be
highly
enabling.
Here,
we
describe
photoactivation
ambiphilic
C1
units
generate
α-bimetalloid
radicals
using
only
Lewis
base
and
light
source
directly
activate
C–I
bond.
Interception
these
transient
with
various
SOMOphiles
rapid
synthesis
organic
scaffolds
(B,
Si,
Ge)
orthogonal
activation.
In-depth
theoretical
mechanistic
studies
reveal
prominent
role
2,6-lutidine
forming
photoactive
charge
transfer
complex
stabilizing
situ
generated
iodine
radicals,
as
well
influential
boron
p-orbital
activation/weakening
This
simple
efficient
methodology
enabled
expedient
access
functionalized
3D
frameworks
can
further
derivatized
available
technologies
C–B
C–Si
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 11, 2024
Abstract
While
polyborylated
alkenes
are
being
recognized
for
their
elevated
status
as
highly
valuable
reagents
in
modern
organic
synthesis,
allowing
efficient
access
to
a
diverse
array
of
transformations,
including
the
formation
C−C
and
C‐heteroatom
bonds,
potential
energy‐transfer
reactive
groups
has
remained
unexplored.
Yet,
this
holds
key
generating
elusive
biradical
species,
which
can
be
captured
by
olefins,
thereby
leading
construction
new
highly‐borylated
scaffolds.
Herein,
we
report
designed
strategy
photosensitized
[2+2]‐cycloadditions
poly‐borylated
with
various
olefins
enabling
regioselective
synthesis
cyclobutane
motifs,
1,1‐di‐,
1,1,2‐tri‐,
1,1,2,2‐tetra‐borylated
cyclobutanes.
In
fact,
these
compounds
belong
family
that
presently
lacks
synthetic
pathways.
Interestingly,
when
α‐methylstyrene
was
used,
reaction
involves
an
interesting
1,5‐hydrogen
atom
transfer
(HAT).
Mechanistic
deuterium‐labeling
studies
have
provided
insight
into
outcome
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ‐lactones.
