The Chemical Record,
Journal Year:
2024,
Volume and Issue:
24(3)
Published: Feb. 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.
Organic & Biomolecular Chemistry,
Journal Year:
2018,
Volume and Issue:
16(7), P. 1050 - 1064
Published: Jan. 1, 2018
Recently,gem-diborylalkanes
have
attracted
much
attention
as
versatile
building
blocks
and
fundamental
intermediates
in
organic
synthesis,
because
they
enable
multiple
C–C
bond
construction
further
transformation
at
C–B
bonds.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 17, 2025
Rigid
bicyclic
hydrocarbons
have
emerged
as
important
building
blocks
in
the
drug
discovery
industry.
Despite
progress
this
general
area,
bicyclo[2.1.0]pentanes
(housanes)
are
an
understudied
class
of
molecules.
Herein
we
report
unconventional
synthesis
borylated
housanes.
Our
method
features
a
broad
scope
and
high
diastereoselectivities
versatile
intermediates.
The
route
involves
strain-release
diboration
bicyclo[1.1.0]butane
intramolecular
deborylative
alkylation.
versatility
bridgehead
boronic
ester
was
demonstrated
several
functionalizations.
Lastly,
mechanism
reaction
investigated,
unusual
stereospecific
diastereoselective
ring
expansion
uncovered.
Advanced Synthesis & Catalysis,
Journal Year:
2017,
Volume and Issue:
360(7), P. 1306 - 1327
Published: Dec. 6, 2017
Abstract
gem
‐Diborylalkanes
have
emerged
as
efficient
reagents
for
synthesizing
organoboron
compounds
through
selective
C−C
bond‐forming
reactions.
Activation
of
the
1,1‐diborylalkanes
generates
carbanions
with
enhanced
stability
that
are
able
to
react
a
series
electrophiles,
carbonyl
compounds,
imines
and
epoxides
promote
formation
new
bond.
These
sets
reactions
become
general
wide
range
substrates
they
can
be
understood
by
alternative
mechanisms
justify
potential
use
these
reagents.
The
C–C(B)
bonds
achieved
chemo‐,
diastereo‐
enantioselectivity,
because
nucleophilc
α‐boryl
or
α‐diboryl
attack
in
stereoselective
manner,
means
catalyst
involved.
synthesis
‐diborylalkanes
has
also
been
promoted
innovative
methods
facilitates
access
multiborylated
different
substituents
properties.
magnified
image
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
11(1), P. 1 - 18
Published: Dec. 10, 2020
Multi(boronate)
esters
have
been
attracting
increasing
attention
as
versatile
building
blocks
for
the
succinct
and
precise
synthesis
of
complex
molecules.
However,
there
are
a
limited
number
efficient
synthetic
procedures
available.
In
this
respect,
direct
multiboration
alkenes
alkynes
is
undoubtedly
an
ideal
route
their
synthesis.
During
past
30
years,
catalytic
systems
based
on
transition-metals,
organophosphines,
bases,
even
catalyst-free
systems,
with
heat
or
light
irradiation
straightforward
preparation
from
developed.
different
numbers
(up
to
4)
positional
relationships
adjacent
boron
moieties
were
obtained,
which
summarized
discussed
herein.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(39), P. 12930 - 12934
Published: July 2, 2018
We
report
the
successful
generation
of
(diborylmethyl)zinc(II)
species
by
transmetallation
beteween
isolable
(diborylmethyl)lithium
and
zinc(II)
halide
(X=Br,
Cl)
their
application
in
synthesis
enantioenriched
gem-diborylalkanes
bearing
a
stereogenic
center
at
β-position
diboryl
groups
an
asymmetric
allylic
substitution
reaction.
The
reaction
has
broad
substrate
scope,
various
can
be
obtained
good
yields
with
excellent
enantioselectivity.
Further
elaboration
provides
access
to
diverse
set
valuable
chiral
building
blocks.
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(8), P. 6890 - 6895
Published: June 28, 2019
The
highly
enantioselective
copper-catalyzed
three-component
boroacylation
of
1,1-disubstituted
allenes
is
reported
by
using
a
class
chiral
ligands
(WJ-Phos),
delivering
various
functionalized
organoboron
compounds
bearing
an
all-carbon
stereocenter
in
moderate
to
good
yields
with
high
enantioselectivities.
WJ-Phos
ferrocene-derived
sulfinamide
phosphine
ligand
and
can
be
easily
synthesized
gram-scale
from
readily
available
starting
materials
short
steps.
salient
features
this
reaction
include
yields,
enantioselectivities,
synthesis,
diverse
synthetic
transformations,
the
development
new
ligand.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(16), P. 10660 - 10680
Published: Aug. 12, 2021
Recent
years
have
witnessed
an
increase
in
the
popularity
of
α-boryl
organometallic
reagents
as
versatile
nucleophiles
asymmetric
synthesis.
These
compounds
been
adopted
chemo-
and
stereoselective
coupling
reactions
with
a
number
different
electrophiles.
The
resulting
enantioenriched
boronic
esters
can
be
applied
stereospecific
carbon-carbon
or
carbon-heteroatom
bond
construction
reactions,
enabling
two-step
strategy
for
complex
structures
high
efficiency
functional
group
compatibility.
Due
to
these
reasons,
tremendous
effort
has
devoted
preparation
enantiomerically
enriched
development
related
racemic
prochiral
materials.
In
this
review,
we
describe
enantio-
diastereoselective
that
involve
starting
materials
products
showcase
their
synthetic
utility.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(2), P. 1069 - 1077
Published: Jan. 4, 2021
We
report
a
copper-catalyzed
enatiotopic-group-selective
allylation
of
gem-diborylalkanes
with
allyl
bromides.
The
combination
copper(I)
bromide
and
H8-BINOL
derived
phosphoramidite
ligand
proved
to
be
the
most
effective
catalytic
system
provide
various
enantioenriched
homoallylic
boronate
esters,
containing
boron-substituted
stereogenic
center
that
is
solely
from
gem-diborylalkanes,
in
good
yields
high
enantiomeric
ratios
under
mild
conditions.
Experimental
theoretical
studies
have
been
conducted
elucidate
reaction
mechanism,
revealing
how
transmetalation
chiral
copper
complex
occurs
generate
α-borylalkyl-copper
species
for
first
time.
Additional
synthetic
applications
synthesis
building
blocks
are
also
included.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(14)
Published: Feb. 1, 2023
This
report
describes
the
unprecedented
electrooxidation
of
a
solvent
(e.g.,
DMF)-ligated
B2
cat2
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
gem-bromides
paired
electrolysis
developed
first
time,
affording
range
versatile
gem-diborylalkanes,
which
are
widely
used
synthetic
society.
Notably,
reaction
approach
scalable,
transition-metal-free,
requires
no
external
activator.
