Angewandte Chemie,
Год журнала:
2023,
Номер
136(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
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
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 15850 - 15859
Опубликована: Май 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
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 20, 2024
Abstract
The
stereoselective
cyclopropanation
of
olefins
with
“boron
ylide”
is
disclosed
for
the
first
time,
providing
a
modular
strategy
synthesis
stereospecific
diboryl‐functionalized
cyclopropanes.
chiral
gem
‐diborylcyclopropanes
are
synthesized
excellent
enantioselectivity
aid
auxiliary.
Based
on
powerful
transformable
ability
boryl
group,
those
challenging
multi‐quaternary
carbon
centers
in
cyclopropane
units
have
been
facilely
constructed
stereoselectivity.
Control
experiments
indicate
that
groups
necessary
both
chemoselectivity
and
stereoselectivity
control.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 2, 2024
Abstract
Epoxides,
as
a
prominent
small
ring
O
-heterocyclic
and
the
privileged
pharmacophores
for
medicinal
chemistry,
have
recently
represented
an
ideal
substrate
development
of
single-atom
replacements.
The
previous
-to-
C
replacement
strategy
epoxides
to
date
typically
requires
high
temperatures
achieve
low
yields
lacks
range
functional
group
tolerance,
so
achieving
this
oxygen-carbon
exchange
remains
formidable
challenge.
Here,
we
report
silver-catalyzed
direct
conversion
into
trifluoromethylcyclopropanes
in
single
step
using
trifluoromethyl
N
-triftosylhydrazones
carbene
precursors,
thereby
via
tandem
deoxygenation/[2
+
1]
cycloaddition.
reaction
shows
broad
tolerance
groups,
allowing
routine
cheletropic
olefin
synthesis
net
reaction.
utility
method
is
further
showcased
with
late-stage
diversification
derived
from
bioactive
natural
products
drugs.
Mechanistic
experiments
DFT
calculations
elucidate
mechanism
origin
chemo-
stereoselectivity.
Organic Letters,
Год журнала:
2023,
Номер
25(50), С. 9020 - 9024
Опубликована: Дек. 8, 2023
This
study
presents
a
novel
method
for
the
regioselective
coupling
of
gem-difluorinated
cyclopropanes
with
gem-diborylmethane,
utilizing
Pd-catalyst
system.
innovative
approach
enables
synthesis
2-fluoroalkenyl
monoboronate
scaffolds
high
Z-selectivity.
The
resulting
products
undergo
further
transformations,
including
oxidation,
Suzuki
cross-coupling,
and
trifluoroborylation,
all
which
are
achieved
good
yields.
work
introduces
valuable
synthetic
pathway
to
access
important
fluorinated
compounds
various
applications
in
organic
chemistry.
Organic Letters,
Год журнала:
2024,
Номер
26(18), С. 3822 - 3827
Опубликована: Апрель 26, 2024
Lithiated
1,1-diborylalkanes
have
been
used
as
nucleophilic
coupling
partners
with
a
range
of
oxygen-based
electrophiles,
including
esters,
carbonyls,
and
epoxides.
However,
their
reactivity
nitrogen-based
such
aziridines,
has
remained
relatively
understudied.
Herein,
we
show
that
lithiated
react
α-halo
α-tosyl
aziridines
to
yield
borylated
(aminomethyl)cyclopropanes–a
privileged
scaffold
within
medicinal
chemistry.
The
reaction
displays
high
levels
diastereoselectivity,
enabling
careful
control
up
three
stereocenters
single
transformation.
DFT
studies
provide
insight
into
the
mechanism,
which
diverges
from
observed
analogous
epihalohydrin
starting
materials.
Derivatization
were
also
performed
on
products
demonstrate
utility
boron
amine
handles.
A
modular
synthesis
method
for
1,4-diketones
has
been
developed.
Utilizing
inexpensive
carboxylic
acid
esters
as
carbonyl
sources
and
tetraborylethane
(TBE)
a
nucleophilic
reagent,
one-pot
strategy
constructing
two
C-C
bonds
was
established.
Notably,
this
reaction
proceeds
without
the
involvement
of
transition
metals
exhibits
excellent
functional
group
compatibility.
diverse
array
α-substituted
were
synthesized
using
various
electrophiles
capture.
The
carbanion
derived
from
chlorodiborylmethane
can
act
as
a
soft
nucleophile,
while
the
halogen
substituent
subsequently
function
leaving
group.
Taking
advantage
of
this
feature,
we
herein
have
developed
an
efficient
synthesis
gem-diborylcyclopropyl
ketones
diverse
range
enone
substrates.
We
also
demonstrated
synthetic
utility
protocol
by
leveraging
highly
transformable
nature
cyclopropyl
moiety
and
C-B
bonds.
Herein
we
report
a
diastereoselective
synthesis
of
boryl-substituted
vinylcyclopropanes,
class
highly
valuable
synthetic
building
blocks,
via
deborylative
cyclization
geminal
diboron
compounds.
The
method
exhibits
broad
functional
group
tolerance
and
accommodates
diverse
alkyl
aryl
α-substituents.
diastereoselectivity
is
primarily
governed
by
the
α-substituent
(alkyl
vs
aryl),
while
olefin
geometry
in
side
chain
has
secondary
influence.
Mechanistic
studies
indicated
distinct
pathways:
concerted
process
for
substrates
carbanion
intermediate
derivatives.
Synthetic
utility
products
was
also
demonstrated.
