Abstract
Recently,
electrochemical
methods
have
been
harnessed
as
a
transition
metal‐free
strategy
for
borylation
reactions
in
the
synthesis
of
organoboron
compounds.
This
article
reviews
C−C
and
C−Het
bonds,
offering
systematic
discussion
C−C,
C−N,
C−O,
C−S
bond
reactions.
These
transformations
are
applied
to
substrates
including
ammonium
salts,
aryl
azo
sulfones,
carboxylic
acids,
arylhydrazines,
nitroarenes,
alcohols,
thioethers,
showcasing
broad
compatibility.
Additionally,
review
discusses
reaction
mechanisms,
scalability,
practical
applications
these
strategies.
The
concludes
by
outlining
future
research
directions
reactions,
aiming
at
expending
their
incorporating
boron
into
wider
array
organic
compounds,
challenging
unactivated
C−F
borylations.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(27)
Опубликована: Фев. 21, 2023
In
photo-induced
olefin
synthesis,
the
photocatalysts
with
high
triplet
energy
could
cause
isomerization
of
olefins.
This
study
demonstrates
a
new
quinoxalinone
photocatalytic
system
for
highly
stereoselective
alkenes
preparation
from
alkenyl
sulfones
and
alkyl
boronic
acids.
Our
photocatalyst
not
convert
thermodynamically
favored
E-olefin
to
Z-olefin,
guaranteeing
E-configuration
selectivity
reaction.
There
is
weak
interaction
between
acids
according
NMR
experiments,
probably
decreasing
oxidation
potential
can
be
further
extended
allyl
alkynyl
give
corresponding
alkynes.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(4)
Опубликована: Дек. 8, 2023
Abstract
Boronate
rearrangements,
such
as
the
Matteson
and
Petasis
reactions,
are
valuable
metal‐free
reactions
for
transfer
of
carbo
group
on
boron
to
intramolecular
electrophilic
sites.
However,
only
highly
reactive
electrophiles
suitable,
ketones
too
inactive
those
boronate
rearrangements
due
high
energy
barriers.
We
disclose
here
1,3‐boronate
rearrangement
ketones,
which
a
barrier
(44.9
kcal/mol)
is
prohibitory
thermal
in
ground
state.
The
reaction
enabled
by
key
keto‐enol‐boronate
bidentate
complex
formation
situ,
absorbs
visible
light
reach
excited
state
chemoselective
ketones.
Experimental
computational
investigations
exclude
free
radical
intermediates
from
organoboronates.
aryl,
alkenyl,
alkyl
boronic
acids
react
with
various
1,3‐diketones
driven
irradiation
construct
structurally
diverse
β‐keto
tertiary
alcohols
under
conditions.
demonstrates
substrate
diversity
58
examples,
yields
up
98
%,
it
suitable
gram‐scale
synthesis.
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.
Abstract
Recently,
electrochemical
methods
have
been
harnessed
as
a
transition
metal‐free
strategy
for
borylation
reactions
in
the
synthesis
of
organoboron
compounds.
This
article
reviews
C−C
and
C−Het
bonds,
offering
systematic
discussion
C−C,
C−N,
C−O,
C−S
bond
reactions.
These
transformations
are
applied
to
substrates
including
ammonium
salts,
aryl
azo
sulfones,
carboxylic
acids,
arylhydrazines,
nitroarenes,
alcohols,
thioethers,
showcasing
broad
compatibility.
Additionally,
review
discusses
reaction
mechanisms,
scalability,
practical
applications
these
strategies.
The
concludes
by
outlining
future
research
directions
reactions,
aiming
at
expending
their
incorporating
boron
into
wider
array
organic
compounds,
challenging
unactivated
C−F
borylations.
