Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 7, 2024
Abstract
A
strategy
for
the
photosensitized
[2+2]‐cycloaddition
between
styrenyl
dihaloboranes
and
unactivated
allylamines
to
access
cyclobutylboronates
with
control
of
stereochemistry
regiochemistry
is
presented.
The
success
reaction
relies
on
temporary
coordination
in
situ
generated
amines
under
mild
conditions.
In
addition,
cyclobutanes
varying
substitution
patterns
have
been
prepared
using
N
‐heterocycles
as
directing
group.
Manipulation
C−B
bond
allows
synthesis
a
diverse
class
from
simple
precursors.
Moreover,
these
reactions
lead
complex
heteroaromatic
compounds,
which
significant
utility
medicinal
chemistry.
Finally,
dearomative
[4+2]‐cycloaddition
naphthalenes
boron‐enabled
tethering
has
also
uncovered
synthesize
3‐dimensional
borylated
building
blocks.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 25, 2025
Arylidenecyclobutanes
are
readily
accessible
and
versatile
reagents
in
synthetic
chemistry
due
to
the
multifaceted
reactivity
exhibited
by
their
alkene
strained
cyclobutane
moieties.
However,
metal-catalyzed
enantioselective
functionalization
of
arylidenecyclobutanes,
particularly
controllable
ring-retaining
ring-opening
reactions,
is
rarely
explored.
Considering
utility
enantioenriched
organoboronate
compounds,
herein
we
report
ligand-controlled
copper-catalyzed
hydroboration
dihydroboration
reactions
arylidenecyclobutanes
that
afford
chiral
α-cyclobutyl
benzylboronate
1,5-diboronate
compounds
with
high
enantioselectivity
when
(S)-DTBM-Segphos
(S,S)-Ph-BPE
employed,
respectively.
Mechanistic
studies
reveal
process
via
β-C
elimination
significantly
slower
than
arylidenecyclopropanes
presence
CuOAc
(S,S)-Ph-BPE.
The
these
two
protocols
further
demonstrated
through
conducting
various
stereospecific
site-selective
transformations
organoboron
products,
including
concise
synthesis
bioactive
molecules.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 9, 2025
Mechanistic
investigations
of
prospective
intermediates
in
copper-catalyzed
cross-coupling
reactions
with
alkyllithium-activated
alkylboronic
esters
are
described.
Complexes
between
(NHC)copper
and
the
borate
salts
were
characterized
by
X-ray
crystallography
NMR,
rate
intramolecular
transmetalation
an
alkyl
group
from
boron
to
copper
was
measured.
Derived
activation
parameters
correlated
those
determined
DFT
analysis
give
insight
into
mechanism
stereospecific
transmetalation.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: May 30, 2025
Chiral
germanium
centers
are
historically
undervalued
due
to
their
extremely
limited
synthetic
accessibility.
Although
shares
similar
chemical
properties
with
silicon,
synthesizing
chiral
proves
significantly
more
challenging.
To
facilitate
rapid
access
centers,
we
develop
two
strategies:
deborylative
alkylation
of
chlorides
and
copper-catalyzed
diol
desymmetrization.
The
α-boryl
carbanion
is
demonstrated
be
an
exceptional
coupling
partner
for
chloride,
yielding
1,3-prochiral
diols,
which
subsequently
undergo
desymmetrization
afford
centers.
By
combining
these
methodologies,
successfully
transform
simple
tetrachloride
into
a
center
in
merely
four
steps,
representing
significant
advancement
main-group
element
chirality.
Additionally,
this
strategy
efficiently
facilitates
the
construction
silicon-stereogenic
as
well.
Subsequent
deoxygenative
cross-coupling
reactions
products
further
expand
scope
organogermanium
chemistry,
revealing
entirely
new
possibilities.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 13, 2024
Non-directed
regioselective
activation
of
bis(boronic
esters),
followed
by
functionalization,
is
reported.
A
bulky
activator
shown
to
selectively
activate
the
less
hindered
boronic
ester
enabling
it
undergo
stereospecific
cross-coupling
a
variety
electrophiles.
This
steric-based
regioselectivity
provides
simple
and
efficient
method
prepare
highly
functionalized,
enantiomerically
enriched
products
starting
from
alkenes.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 7, 2024
A
strategy
for
the
photosensitized
[2+2]-cycloaddition
between
styrenyl
dihaloboranes
and
unactivated
allylamines
to
access
cyclobutylboronates
with
control
of
stereochemistry
regiochemistry
is
presented.
The
success
reaction
relies
on
temporary
coordination
in
situ
generated
amines
under
mild
conditions.
In
addition,
cyclobutanes
varying
substitution
patterns
have
been
prepared
using
N-heterocycles
as
directing
group.
Manipulation
C-B
bond
allows
synthesis
a
diverse
class
from
simple
precursors.
Moreover,
these
reactions
lead
complex
heteroaromatic
compounds,
which
significant
utility
medicinal
chemistry.
Finally,
dearomative
[4+2]-cycloaddition
naphthalenes
boron-enabled
tethering
has
also
uncovered
synthesize
3-dimensional
borylated
building
blocks.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(25)
Published: April 19, 2024
Abstract
The
reaction
regioselectivity
of
gem
‐difluoroalkenes
is
dependent
on
the
intrinsic
polarity.
Thus,
reversal
addition
remains
a
formidable
challenge.
Herein,
we
described
an
unprecedented
hydrogen
atom
transfer
(HAT)
to
triggered
by
Fe−H
species
for
formation
difluoroalkyl
radicals.
Hydrogenation
in
situ
generated
radicals
gave
difluoromethylated
products.
Mechanism
experiments
and
theoretical
studies
revealed
that
kinetic
effect
irreversible
HAT
process
resulted
this
scenario,
leading
less
stable
α
‐difluoroalkyl
radical
regioisomer.
On
basis
new
‐difluoroalkene,
iron‐promoted
hydrohalogenation
efficient
synthesis
aliphatic
chlorodifluoromethyl‐,
bromodifluoromethyl‐
iododifluoromethyl‐containing
compounds
was
developed.
Particularly,
novel
provided
large‐scale
access
various
iododifluoromethylated
high
value
synthetic
application.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(39)
Published: June 26, 2024
Abstract
Non‐directed
regioselective
activation
of
bis(boronic
esters),
followed
by
functionalization,
is
reported.
A
bulky
activator
shown
to
selectively
activate
the
less
hindered
boronic
ester
enabling
it
undergo
stereospecific
cross‐coupling
a
variety
electrophiles.
This
steric‐based
regioselectivity
provides
simple
and
efficient
method
prepare
highly
functionalized,
enantiomerically
enriched
products
starting
from
alkenes.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 7, 2024
Abstract
A
strategy
for
the
photosensitized
[2+2]‐cycloaddition
between
styrenyl
dihaloboranes
and
unactivated
allylamines
to
access
cyclobutylboronates
with
control
of
stereochemistry
regiochemistry
is
presented.
The
success
reaction
relies
on
temporary
coordination
in
situ
generated
amines
under
mild
conditions.
In
addition,
cyclobutanes
varying
substitution
patterns
have
been
prepared
using
N
‐heterocycles
as
directing
group.
Manipulation
C−B
bond
allows
synthesis
a
diverse
class
from
simple
precursors.
Moreover,
these
reactions
lead
complex
heteroaromatic
compounds,
which
significant
utility
medicinal
chemistry.
Finally,
dearomative
[4+2]‐cycloaddition
naphthalenes
boron‐enabled
tethering
has
also
uncovered
synthesize
3‐dimensional
borylated
building
blocks.
