ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 5156 - 5166
Published: March 21, 2024
Alkylidenecyclopropanes
(ACPs)
contain
a
highly
strained
cyclopropane
ring
and
an
exomethylene
group.
The
transition
metal-catalyzed
borylative
difunctionalization
of
ACPs
provides
swift
access
to
useful
building
blocks.
However,
most
existing
reactions
lead
1,3-difunctionalization
products.
ring-opening
1,1-difunctionalization
has
not
been
reported.
Herein,
we
report
diborylation
for
the
synthesis
γ,δ-unsaturated
1,1-diborylated
compounds
using
our
developed
SNIr-X
catalyst.
It
represents
rare
progress
in
gem-diborylation
ACPs.
Combined
experimental
computational
studies
reveal
substrate
scope
mechanism
this
transformation.
1,1-diborylation
reaction
proceeds
via
Ir(I)/Ir(III)-catalyzed
borylation/Ir-migration/borylation
process.
Control
experiments
density
functional
theory
(DFT)
calculations
indicate
that
direct
hydrogen
migration
involving
M–H
species
should
be
involved
diaryl-substituted
substrate,
while
monoaryl-substituted
proceeded
β-H
elimination-induced
chain-walking
In
addition,
two
other
types
substrates
was
investigated.
Substituted
methylenecyclopropanes
(MCPs)
produced
1,4-diborylated
products,
cyclopropyl-substituted
gave
1,7-diborylation
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(11), P. 4107 - 4112
Published: May 7, 2020
Simple
nucleophiles
with
structural
similarities
to
known
hydroboration
catalysts
can
readily
mediate
the
formation
of
BH3
and
borohydride
species
from
pinacolborane
(HBpin).
Alkyne
alkene
reactions
were
successfully
mediated
by
through
generation,
BH3-catalyzed
found
dominate
catalysis.
NMR
spectroscopy
kinetic
analyses
showed
that
NaOtBu,
Na[N(SiMe3)2],
nBu2Mg,
nBuLi
only
promoted
not
"true"
catalysts.
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.
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.
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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(3)
Published: Dec. 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
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(4), P. 2305 - 2314
Published: Jan. 19, 2023
While
1,1-diboryl
(gem-diboryl)
compounds
are
valuable
synthetic
building
blocks,
currently,
related
studies
have
mainly
focused
on
those
alkanes
without
a
hetero
functional
group
in
the
α-position.
gem-Diboryl
with
an
α-hetero
substituent,
though
highly
versatile,
been
limitedly
accessible
and
thus
rarely
utilized.
Herein,
we
developed
first
α-dihydroboration
of
heteroalkynes
leading
to
efficient
construction
gem-diboryl,
hetero-,
tetra-substituted
carbon
centers.
This
straightforward,
practical,
mild,
atom-economic
reaction
is
attractive
complement
conventional
multistep
strategy
relying
deprotonation
gem-diborylmethane
by
strong
base.
Specifically,
[Ir(cod)(OMe)]2
was
found
be
uniquely
effective
for
this
process
thioalkynes,
excellent
α-regioselectivity
when
delivering
two
boryl
groups,
which
remarkable
view
many
competitive
paths
including
monohydroboration,
1,2-dihydroboration,
dehydrodiboration,
triboration,
tetraboration,
etc.
Control
experiments
combined
DFT
calculations
suggested
that
involves
sequential
hydroboration
events.
The
second
requires
higher
energy
barrier
due
severe
steric
repulsion
generating
congested
α-sulfenyl
gem-diboryl
center,
structural
motif
almost
unknown
before.
Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(2), P. 777 - 777
Published: Jan. 1, 2023
A
novel
synthesis
of
halogenated
gem-diboronates
(X-CR(Bpin)2)
was
developed.The
reagents
are
stable
and
easy
to
prepare
in
a
large
scale.Tetra-substituted
can
be
prepared
high
yields
when
using
alkylsubstituted
gem-dihalides,
providing
new
strategy
for
the
gem-diboron
compounds.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 976 - 981
Published: Jan. 1, 2025
Triethoxysilane
was
found
to
be
an
efficient
catalyst
for
the
synthesis
of
E-alkenyl-
and
alkyl-di-boronate
esters
by
single
sequential
hydroboration
terminal
alkynes,
respectively,
with
pinacolborane.
Mechanistic
studies
support
that
formation
diboronate
proceeds
a
double
pathway
steric
electronic
profile
at
Si
being
key
enabling
second
step.
Weak
non-covalent
interactions
involving
C≡C
or
C═C
bonds
in
alkynes
alkenylboronate
have
been
identified
as
responsible
substrate
activation
toward
addition
HBPin.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(6), P. 3190 - 3197
Published: Feb. 25, 2021
The
activation
and
functionalization
of
carbon–fluorine
bonds
represent
a
significant
synthetic
challenge,
given
the
high
thermodynamic
barrier
to
C–F
bond
cleavage.
Stoichiometric
hydridoborane-mediated
has
recently
emerged,
but
is
yet
be
rendered
catalytic.
Herein,
borane-catalyzed
coupling
alkyl
fluorides
with
arenes
(carbon–carbon
formation)
carboxylic
acids
(carbon–oxygen
been
developed
using
transborylation
reactions
achieve
catalytic
turnover.
Successful
C–C
C–O
across
variety
structurally
electronically
differentiated
was
achieved
9-borabicyclo[3.3.1]nonane
(H-B-9-BBN)
as
catalyst
pinacolborane
(HBpin),
broad
functional
group
tolerance.
Experimental
computational
studies
suggest
mechanistic
dichotomy
for
carbon–carbon
carbon–oxygen
reactions.
B–F
(B–F/B–H
metathesis)
between
F-B-9-BBN
HBpin
enabled
turnover
formation,
whereas
direct
exchange
fluoride
acyloxyboronic
ester
(C–F/B–O
proposed
coupling,
where
H-B-9-BBN
catalyzed
dehydrocoupling
acid
HBpin.