Research Square (Research Square),
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Abstract
Herein,
we
report
a
rare
example
of
organocatalyzed
skeletal
editing
unstrained
rings
(n
=
4–8)
to
ring-expansion
via
Wolff-type
rearrangement
and
through
regioselective
fixation
carbon
nitrogen
atom.
Strategy
employed
2-formylarylboronic
acid
as
C-B
surrogate
TMSN3
an
exogenous
single
source;
allowed
the
de
novo
rapid
synthesis
BN
isosteres
by
forging
C-C,
C-N
B-N
bonds
under
operation.
The
developed
method
proved
be
compatible
with
wide
substrate
scope
(50
examples)
including
cyclic
ketones
diverse
heterocycles
afforded
1C
ring
expanded
[1,2]-azaborines.
Reaction
was
also
effective
acyclic
give
naphthalene
isosteres.
Control
experiments
DFT
study
dictate
plausible
reaction
pathways
following
[1,2]-C-C/C-H
shift,
analogous
Wolff
rearrangement.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 19499 - 19508
Published: July 3, 2024
The
design
of
small
molecules
with
unique
geometric
profiles
or
molecular
connectivity
represents
an
intriguing
yet
neglected
challenge
in
modern
organic
synthesis.
This
is
compounded
when
emphasis
placed
on
the
preparation
new
chemotypes
that
have
distinct
and
practical
functions.
To
expand
structural
diversity
boron-containing
heterocycles,
we
report
herein
novel
monocyclic
hemiboronic
acids,
diazaborines.
These
compounds
enabled
study
a
pseudoaromatic
boranol-containing
(B-OH)
ring
free
influence
from
appended
aromatic
system.
Synthetic
spectroscopic
studies
provided
insight
into
character,
Lewis
acidic
nature,
chemical
reactivity,
ability
exocyclic
B-OH
unit
to
participate
hydroxy
exchange,
suggesting
their
use
organocatalysis
as
reversible
covalent
inhibitors.
Moreover,
density
functional
theory
nucleus-independent
shift
calculations
reveal
character
boroheterocyclic
increased
significantly
comparison
known
bicyclic
benzodiazaborines
(naphthoid
congeners),
consequently
leading
attenuated
acidity.
Direct
well-established
biaryl
isostere,
2-phenylphenol,
through
X-ray
crystallographic
analysis
reveals
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: July 9, 2024
In
this
work,
we
describe
an
efficient
and
modular
method
for
enantiodivergent
accessing
P(V)-stereogenic
molecules
by
utilizing
the
catalytic
atroposelective
Catellani-type
C-H
arylation/desymmetric
intramolecular
N-arylation
cascade
reaction.
The
enantioselectivity
of
protocol
was
proved
to
be
tuned
polarity
solvent,
thus
providing
a
wide
range
both
chiral
enantiomers
in
moderate
good
yields
with
excellent
enantiomeric
excesses.
Noteworthy
is
that
strategy
developed
herein
represents
unprecedented
example
solvent-dictated
inversion
compounds.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
A
palladium/norbornene
(NBE)-catalyzed
2-fold
C-H/C-X
coupling
reaction
of
aryl
iodides
is
reported.
Bromine-substituted
benzimidazoles
were
chosen
as
electrophilic
and
termination
reagents,
the
versatile
polycyclic
aromatic
hydrocarbon
products
successfully
obtained.
The
strategy
overcomes
challenge
catalyst
poisoning
by
heterocyclic
substrates.
In
addition,
imidazole
moiety
in
product
endowed
with
a
localization
role,
thus
enabling
compounds
to
be
applied
wider
synthetic
scenario,
fluorescence
persisted.
Furthermore,
bioactivity
evaluation
has
identified
three
promising
leading
3b,
4e,
4i.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 6, 2025
Herein,
we
report
a
novel
palladium(II)-initiated
borono-Catellani
reaction
that
utilizes
widely
accessible
aryl
boronic
acids
serve
as
both
the
reaction-initiating
and
-terminating
substrates
for
first
time.
The
was
facilitated
by
cooperative
catalysis
between
Pd(OAc)2
NBE,
with
air
serving
oxidizing
agent,
opening
new
venues
developing
Catellani-type
reactions.
Importantly,
this
method
is
compatible
wide
range
of
substrates,
including
naphthaleneboronic
acid,
phenylboric
acid
derivatives,
alkyl
iodides,
under
these
environmentally
friendly
mild
conditions,
thereby
demonstrating
versatile
functional
group
compatibility
synthesis
valuable
polysubstituted
aromatics.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 5, 2025
Two
planar
BN
doped
benzofluorenes
(BN-BkF
and
BN-BjF)
were
synthesized
separately
through
palladium-catalyzed
intramolecular
C-C
or
C-N
coupling
reactions.
The
structures
of
both
BN-BkF
BN-BjF
are
unambiguously
confirmed
by
X-ray
crystallographic
analysis.
Moreover,
the
unit
doping
leads
to
a
much
lower
HOMO
level
higher
LUMO
as
compared
their
carbon
analogues
BkF
BjF.
In
comparison
BjF,
exhibit
blue
shifts
in
ultraviolet-visible
(UV-vis)
absorption
fluorescence
emission
spectra.
Furthermore,
halogenation
afforded
monohalogenated
BN-benzofluorenes
good
yields.
These
can
serve
convenient
intermediates
for
reactions
yield
series
functionalized
BN-benzofluorene
derivatives.
UV-vis
spectroscopies
dichloromethane
these
derivatives
studied,
photophysics
compounds
exhibited
high
degree
substituent
dependency.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(41)
Published: July 9, 2024
Abstract
In
this
work,
we
describe
an
efficient
and
modular
method
for
enantiodivergent
accessing
P(V)‐stereogenic
molecules
by
utilizing
the
catalytic
atroposelective
Catellani‐type
C−H
arylation/desymmetric
intramolecular
N
‐arylation
cascade
reaction.
The
enantioselectivity
of
protocol
was
proved
to
be
tuned
polarity
solvent,
thus
providing
a
wide
range
both
chiral
enantiomers
in
moderate
good
yields
with
excellent
enantiomeric
excesses.
Noteworthy
is
that
strategy
developed
herein
represents
unprecedented
example
solvent‐dictated
inversion
compounds.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
27(1), P. 121 - 128
Published: Dec. 30, 2024
The
enantioselective
synthesis
of
P(V)-stereogenic
compounds
has
emerged
as
an
interesting
research
topic
primarily
due
to
their
significant
biological
activity
and
broad
application
prospects.
Herein,
we
disclose
a
method
for
the
construction
from
prochiral
phosphinamides
aryl
iodides
via
palladium-
chiral
norbornene-catalyzed
desymmetric
annulation.
were
formed
with
scope
excellent
enantiomeric
excesses.
It
is
noteworthy
that
synthetic
value
this
procedure
was
proven
by
variety
transition
metal-catalyzed
cross-coupling
reactions
using
C–Br
bond
on
product
versatile
linchpin
electrophile.
