Green Synthesis and Catalysis,
Journal Year:
2022,
Volume and Issue:
5(1), P. 68 - 72
Published: Dec. 14, 2022
A
novel,
efficient
and
pragmatic
method
to
prepare
gem-diboron
products
with
vicinal
tertiary/quaternary
stereocenters
using
LiTMP-mediated
1,6-conjugate
addition
of
gem-diborylalkanes
para-quinone
methides
was
described
for
the
first
time.
The
results
showed
that
various
tertiary
quaternary
could
be
formed
within
15
min
at
ambient
temperature.
This
simple
protocol
has
also
been
applied
synthesis
analogue
Bedaquiline.
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:
2024,
Volume and Issue:
146(23), P. 15850 - 15859
Published: May 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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 11, 2024
Abstract
While
polyborylated
alkenes
are
being
recognized
for
their
elevated
status
as
highly
valuable
reagents
in
modern
organic
synthesis,
allowing
efficient
access
to
a
diverse
array
of
transformations,
including
the
formation
C−C
and
C‐heteroatom
bonds,
potential
energy‐transfer
reactive
groups
has
remained
unexplored.
Yet,
this
holds
key
generating
elusive
biradical
species,
which
can
be
captured
by
olefins,
thereby
leading
construction
new
highly‐borylated
scaffolds.
Herein,
we
report
designed
strategy
photosensitized
[2+2]‐cycloadditions
poly‐borylated
with
various
olefins
enabling
regioselective
synthesis
cyclobutane
motifs,
1,1‐di‐,
1,1,2‐tri‐,
1,1,2,2‐tetra‐borylated
cyclobutanes.
In
fact,
these
compounds
belong
family
that
presently
lacks
synthetic
pathways.
Interestingly,
when
α‐methylstyrene
was
used,
reaction
involves
an
interesting
1,5‐hydrogen
atom
transfer
(HAT).
Mechanistic
deuterium‐labeling
studies
have
provided
insight
into
outcome
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ‐lactones.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 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.
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 Letters,
Journal Year:
2024,
Volume and Issue:
26(33), P. 7010 - 7014
Published: Aug. 8, 2024
The
development
of
effective
strategies
to
forge
C–O
and
C–S
bonds
in
diverse
chemical
spaces
is
considerable
interest
synthetic
organic
chemistry.
Herein
we
report
a
versatile
approach
for
the
modular
synthesis
structurally
(thio)ethers
(thio)esters
via
homologative
coupling
α-halodiborylmethane
followed
by
transformation
introduced
diborylmethyl
group.
This
method
accommodates
wide
array
oxygen-
sulfur-containing
molecules,
including
biologically
active
compounds.
initial
exhibits
broad
substrate
scope,
while
subsequent
diversification
moiety
enables
access
various
structural
motifs
through
deborylative
alkylation,
Zweifel
olefination,
boron-Wittig
reaction.
protocol
efficiently
generates
diversely
functionalized
(thio)esters,
expanding
toolkit
accessing
relevant
scaffolds.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(35), P. 5213 - 5216
Published: Jan. 1, 2023
gem
-Difluoroallylic
bicyclo[1.1.1]pentanes
were
synthesized
via
visible
light-induced
defluorinative
-difluoroallylation
of
[1.1.1]propellane
under
mild
conditions
with
good
functional
group
tolerance.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(22), P. 4130 - 4134
Published: May 25, 2023
We
report
a
transition-metal-free
deborylative
cyclization
approach
to
synthesize
enantioenriched
secondary
and
tertiary
cyclopropylboronates
using
γ-phosphate-containing
gem-diborylalkanes
derived
from
chiral
epoxides
gem-diborylalkanes.
Our
method
enables
the
synthesis
of
broad
range
in
good
yields
with
excellent
stereospecificity.
demonstrate
versatility
our
by
performing
gram-scale
reaction.
also
show
that
can
be
transformed
into
wide
array
cyclopropane
derivatives
stereospecific
boron-group
transformation.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(50), P. 9020 - 9024
Published: Dec. 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.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(12), P. 1360 - 1366
Published: Feb. 23, 2024
Comprehensive
Summary
The
conversion
of
CF
3
‐alkenes
to
gem
‐difluoroalkenes
using
reductive
cross‐coupling
strategy
has
received
much
attention
in
recent
years,
however,
the
use
green
and
readily
available
reducing
salt
mediate
these
reactions
remains
be
explored.
In
this
work,
a
concise
construction
gem‐
difluoroalkenes,
which
requires
neither
catalyst
nor
metal
agent,
was
established.
Rongalite,
safe
inexpensive
industrial
product,
employed
as
both
radical
initiator
reductant.
This
procedure
compatible
with
linear
cyclic
diaryliodonium
salts,
enabling
wide
variety
substrates
(>70
examples).
utility
approach
demonstrated
through
gram‐scale
synthesis
efficient
late‐stage
functionalizations
anti‐inflammatory
drugs.
