Research Square (Research Square),
Год журнала:
2022,
Номер
unknown
Опубликована: Сен. 19, 2022
Abstract
Alkenyl
boronate
esters
are
important
synthons
for
various
pharmaceuticals,
agrochemicals,
natural
products,
and
material
science.
Direct
alkene
sp2
C-H
bond
borylation
is
highly
valued
its
synthesis.
However,
the
drawbacks
associated
with
chemo-,
regio-
stereoselectivity,
using
late
transition
metal
catalysts,
need
sacrificial
hydrogen
scavengers
impeded
practicability
sustainability.
Herein,
we
utilized
a
3d
complex
as
catalyst
synthesizing
alkenyl
via
dehydrogenative
coupling
of
styrenes
pinacolborane.
Hydrogen
gas
produced
sole
byproduct
without
needing
an
acceptor,
making
process
green
atom-economical.
The
methodology
depicted
excellent
selectivity
towards
over
direct
hydroboration.
Borylation
aromatic
alkenes
aliphatic
ones
was
also
noticed.
Derivatives
products
bioactive
molecules
underwent
successful
diversification.
product
could
be
employed
several
drugs
potential
anticancer
agents.
Thorough
experimental
high-level
computational
studies
were
performed
to
delineate
reaction
pathway.
hemilability
metal-ligand
bifunctionality
ligand
backbone
found
crucial
catalytic
turnover.
Chemical Science,
Год журнала:
2023,
Номер
14(29), С. 7897 - 7904
Опубликована: Янв. 1, 2023
We
developed
a
copper-catalyzed
stereoselective
strategy
for
the
unified
synthesis
of
borylated
methylenecyclobutanes.
The
versatile
boromethylene
unit
greatly
expands
their
structural
diversity
and
potential
in
future
drug
discovery.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(15)
Опубликована: Дек. 3, 2022
When
mono-radical
ipso-cyclization
of
aryl
sulfonamides
tend
to
undergo
Smiles-type
rearrangement
through
aromatization-driven
C-S
bond
cleavage,
diradical-mediated
cyclization
must
perform
in
a
distinct
reaction
pathway.
It
is
interesting
meanwhile
challenging
tune
the
rate
cleavage
achieve
chemically
divergent
(hetero)
visible-light
induced
energy
transfer
(EnT)
pathway
involving
diradical
species.
Herein
based
on
designed
indole-tethered
(hetero)arylsulfonamides
reported
which
involves
and
controllable
an
inherent
bond.
The
combined
experimental
computational
results
have
revealed
that
these
substrates
can
be
controlled
by
tuning
heteroaryl
moieties:
a)
If
(hetero)aryl
thienyl,
furyl,
phenanthryl,
etc.,
radical
coupling
double
dearomative
diradicals
(DDDR)
precedes
over
afford
cyclobutene
fused
indolines
[2+2]-cycloaddition;
b)
if
phenyl,
naphthyl,
pyridyl,
indolyl
DDDR
favored
biaryl
products.
Chemical Science,
Год журнала:
2022,
Номер
14(4), С. 963 - 969
Опубликована: Дек. 21, 2022
There
is
an
increasing
interest
in
cyclobutanes
within
the
medicinal
chemistry
community.
Therefore,
methods
to
prepare
that
contain
synthetic
handles
for
further
elaboration
are
of
interest.
Herein,
we
report
a
new
approach
synthesis
3-borylated
cyclobutanols
via
formal
[3
+
1]-cycloaddition
using
readily
accessible
1,1-diborylalkanes
and
epihalohydrins
or
epoxy
alcohol
derivatives.
1-Substituted
epibromohydrin
starting
materials
provide
access
borylated
containing
substituents
at
three
four
positions
on
cyclobutane
core,
enantioenriched
epibromohydrins
lead
with
high
levels
enantiospecificity
(>98%).
Finally,
derivatization
studies
demonstrate
utility
both
OH
Bpin
handles.
Chemical Science,
Год журнала:
2024,
Номер
15(9), С. 3249 - 3254
Опубликована: Янв. 1, 2024
A
one-step
approach
to
borylated
cyclobutanes
from
amides
of
carboxylic
acids
and
vinyl
boronates
is
elaborated.
The
reaction
proceeds
via
the
thermal
[2
+
2]-cycloaddition
in
situ
-generated
keteniminium
salts.
Chemical Science,
Год журнала:
2023,
Номер
15(3), С. 1098 - 1105
Опубликована: Дек. 11, 2023
In
this
study,
we
employed
a
3d
metal
complex
as
catalyst
to
synthesize
alkenyl
boronate
esters
through
the
dehydrogenative
coupling
of
styrenes
and
pinacolborane.
The
process
generates
hydrogen
gas
sole
byproduct
without
requiring
an
acceptor,
rendering
it
environmentally
friendly
atom-efficient.
This
methodology
demonstrated
exceptional
selectivity
for
borylation
over
direct
hydroboration.
Additionally,
exhibited
preference
borylating
aromatic
alkenes
aliphatic
ones.
Notably,
derivatives
natural
products
bioactive
molecules
successfully
underwent
diversification
using
approach.
served
precursors
synthesis
various
pharmaceuticals
potential
anticancer
agents.
Our
research
involved
comprehensive
experimental
computational
studies
elucidate
reaction
pathway,
highlighting
B-H
bond
cleavage
rate-determining
step.
catalyst's
success
was
attributed
hemilability
metal-ligand
bifunctionality
ligand
backbone.
Angewandte Chemie,
Год журнала:
2022,
Номер
134(38)
Опубликована: Июнь 24, 2022
Abstract
Recently
the
fruitful
merger
of
organoboron
chemistry
and
photocatalysis
has
come
to
forefront
organic
synthesis,
resulting
in
development
new
technologies
access
complex
(non)borylated
frameworks.
Central
success
this
combination
is
control
boron
hybridisation.
Contingent
on
photoactivation
mode,
as
its
neutral
planar
form
or
tetrahedral
boronate
can
be
used
regulate
reactivity.
This
Minireview
highlights
current
state
art
photocatalytic
processes
utilising
compounds,
paying
particular
attention
role
hybridisation
for
target
transformation.
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
radophile
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.
Mechanistic
deuterium-labeling
studies
have
provided
insight
into
outcome
transfer
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ-lactones.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(41)
Опубликована: Май 28, 2024
Abstract
Dearomative
construction
of
multiply‐fused
2D/3D
frameworks,
composed
aromatic
two‐dimensional
(2D)
rings
and
saturated
three‐dimensional
(3D)
rings,
from
readily
available
quinolines
has
greatly
contributed
to
drug
discovery.
However,
dearomative
cycloadditions
in
the
presence
photocatalysts
usually
afford
5,6,7,8‐tetrahydroquinoline
(THQ)‐based
polycycles,
access
1,2,3,4‐THQ‐based
structures
remains
limited.
Herein,
we
present
a
chemo‐,
regio‐,
diastereo‐,
enantioselective
transformation
into
6–6–4‐membered
without
any
catalyst,
through
combination
nucleophilic
addition
borate‐mediated
[2+2]
photocycloaddition.
Detailed
mechanistic
studies
revealed
that
photoexcited
borate
complex,
generated
quinoline,
organolithium,
HB(pin),
accelerates
cycloaddition
suppresses
rearomatization
occurs
conventional
Based
on
our
analysis,
also
developed
further
photoinduced
affording
other
types
frameworks
isoquinoline
phenanthrene.
Communications Chemistry,
Год журнала:
2024,
Номер
7(1)
Опубликована: Июнь 19, 2024
Abstract
Radical-polar
crossover
of
organoborates
is
a
poweful
tool
that
enables
the
creation
two
C-C
bonds
simultaneously.
Small
ring
systems
have
become
essential
motifs
in
drug
discovery
and
medicinal
chemistry.
However,
step-economic
methods
for
their
selective
functionalization
remains
scarce.
Here
we
present
one-pot
strategy
merges
simple
preparation
strained
organoboron
species
with
recently
popularized
polar
radical
borate
derivatives
to
stereoselectively
access
tri-substituted
azetidines,
cyclobutanes
five-membered
carbo-
heterocycles.
Research Square (Research Square),
Год журнала:
2022,
Номер
unknown
Опубликована: Сен. 19, 2022
Abstract
Alkenyl
boronate
esters
are
important
synthons
for
various
pharmaceuticals,
agrochemicals,
natural
products,
and
material
science.
Direct
alkene
sp2
C-H
bond
borylation
is
highly
valued
its
synthesis.
However,
the
drawbacks
associated
with
chemo-,
regio-
stereoselectivity,
using
late
transition
metal
catalysts,
need
sacrificial
hydrogen
scavengers
impeded
practicability
sustainability.
Herein,
we
utilized
a
3d
complex
as
catalyst
synthesizing
alkenyl
via
dehydrogenative
coupling
of
styrenes
pinacolborane.
Hydrogen
gas
produced
sole
byproduct
without
needing
an
acceptor,
making
process
green
atom-economical.
The
methodology
depicted
excellent
selectivity
towards
over
direct
hydroboration.
Borylation
aromatic
alkenes
aliphatic
ones
was
also
noticed.
Derivatives
products
bioactive
molecules
underwent
successful
diversification.
product
could
be
employed
several
drugs
potential
anticancer
agents.
Thorough
experimental
high-level
computational
studies
were
performed
to
delineate
reaction
pathway.
hemilability
metal-ligand
bifunctionality
ligand
backbone
found
crucial
catalytic
turnover.
