Angewandte Chemie,
Год журнала:
2023,
Номер
136(4)
Опубликована: Дек. 8, 2023
Abstract
General
methods
for
the
preparation
of
geminal
bis(boronates)
are
great
interest
due
to
their
widespread
applications
in
organic
synthesis.
While
terminal
gem
‐diboron
compounds
readily
accessible,
construction
sterically
encumbered,
internal
analogues
has
remained
a
prominent
challenge.
Herein,
we
report
formal
umpolung
strategy
access
these
valuable
building
blocks.
The
available
1,1‐diborylalkanes
were
first
converted
into
corresponding
α‐halogenated
derivatives,
which
then
serve
as
electrophilic
components,
undergoing
substitution
with
diverse
array
nucleophiles
form
series
C−C,
C−O,
C−S,
and
C−N
bonds.
This
protocol
features
good
tolerance
steric
hindrance
wide
variety
functional
groups
heterocycles.
Notably,
this
can
also
be
extended
synthesis
diaryl
compounds,
therefore
providing
general
approach
various
types
bis(boronates).
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Дек. 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
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 976 - 981
Опубликована: Янв. 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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(4)
Опубликована: Дек. 8, 2023
Abstract
General
methods
for
the
preparation
of
geminal
bis(boronates)
are
great
interest
due
to
their
widespread
applications
in
organic
synthesis.
While
terminal
gem
‐diboron
compounds
readily
accessible,
construction
sterically
encumbered,
internal
analogues
has
remained
a
prominent
challenge.
Herein,
we
report
formal
umpolung
strategy
access
these
valuable
building
blocks.
The
available
1,1‐diborylalkanes
were
first
converted
into
corresponding
α‐halogenated
derivatives,
which
then
serve
as
electrophilic
components,
undergoing
substitution
with
diverse
array
nucleophiles
form
series
C−C,
C−O,
C−S,
and
C−N
bonds.
This
protocol
features
good
tolerance
steric
hindrance
wide
variety
functional
groups
heterocycles.
Notably,
this
can
also
be
extended
synthesis
diaryl
compounds,
therefore
providing
general
approach
various
types
bis(boronates).
The Chemical Record,
Год журнала:
2024,
Номер
24(3)
Опубликована: Фев. 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.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(10), С. 7280 - 7285
Опубликована: Май 8, 2024
A
practical
and
efficient
method
to
access
polysubstituted
aryl
sulfides
has
been
discovered
via
a
Lewis
acid-catalyzed
reaction
between
alkynyl
sulfide
2-pyrone,
involving
Diels-Alder/retro-Diels-Alder
pathway.
Alkynyl
as
an
electron-rich
dienophile
2-pyrones
electron-poor
dienes
are
conjunctively
transformed
into
series
of
with
broad
functional
group
compatibility
in
good
excellent
yields
(40
examples,
43-88%
yield).
The
robustness
practicality
the
protocol
demonstrated
through
gram-scale
synthesis
ease
transformation
resulting
products.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(33)
Опубликована: Май 31, 2024
Abstract
gem
‐Diborylalkanes
are
highly
valuable
building
blocks
in
organic
synthesis
and
pharmaceutical
chemistry
due
to
their
ability
participate
multi‐step
cross‐coupling
transformations,
allowing
for
the
rapid
generation
of
molecular
complexity.
While
progress
has
been
made
synthetic
metholodology,
construction
β‐tertiary
C(sp
3
)‐rich
‐diborylalkanes
remains
a
challenge
substrate
limitations
steric
hindrance
issues.
An
approach
is
presented
that
utilizes
synergistic
photoredox
copper
catalysis
achieve
efficient
)−C(sp
)
alkyl
N
‐hydroxyphthalimide
esters,
which
can
easily
be
obtained
from
carboxylic
acids,
with
diborylmethyl
species,
providing
series
1°,
2°,
even
3°
β
positions.
Furthermore,
this
also
applied
complex
medicinal
compounds
natural
products,
offering
access
complexity
late‐stage
functionalization
drug
candidates.
Mechanistic
experiments
revealed
Cu(I)
species
participated
both
process
key
bond‐forming
step.
RSC Advances,
Год журнала:
2025,
Номер
15(13), С. 10265 - 10272
Опубликована: Янв. 1, 2025
This
study
introduces
an
efficacious
palladium-catalyzed
method
for
the
regioselective
and
stereoselective
cross-coupling
of
gem
-difluorinated
cyclopropanes
with
array
-diborylalkanes
under
mild
reaction
conditions.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(14), С. 3603 - 3611
Опубликована: Янв. 1, 2023
We
have
developed
a
general
and
easily
accessible
alkynylthio
nucleophile
precursor
to
couple
with
various
carbon
electrophiles,
as
an
attractive
route
for
their
synthesis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 5156 - 5166
Опубликована: Март 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
