The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 19, 2024
Although
the
radical
hydroboration
of
alkenes
with
N-heterocyclic
carbene
(NHC)
borane
is
well
documented,
alkynes,
especially
terminal
remains
challenging.
Herein,
a
photoredox-catalyzed
trans-hydroboration
alkynes
NHC
has
been
developed,
which
provided
various
alkenyl
boron
compounds
in
moderate
to
good
yields.
This
protocol
exhibits
broad
substrate
scope,
as
both
internal
and
were
compatible.
The
synthetic
value
this
method
was
further
demonstrated
by
its
applicability
late-stage
modification
bioactive
molecules.
A
preliminary
mechanism
for
reaction
proposed.
Accounts of Chemical Research,
Год журнала:
2022,
Номер
56(2), С. 169 - 186
Опубликована: Дек. 26, 2022
ConspectusThe
past
decades
have
witnessed
tremendous
progress
on
radical
reactions.
However,
in
comparison
with
carbon,
nitrogen,
oxygen,
and
other
main
group
element
centered
radicals,
the
synthetic
chemistry
of
boron
radicals
was
less
studied,
mainly
due
to
high
electron-deficiency
instability
such
3-center-5-electron
species.
In
1980s,
Roberts
co-workers
found
that
coordination
a
Lewis
base
(amines
or
phosphines)
center
could
form
4-center-7-electron
boryl
(Lewis
base-boryl
LBRs)
are
be
more
stable.
only
limited
applications
were
developed.
2008,
Curran
achieved
breakthrough
discovery
N-heterocyclic
carbene
(NHC)
which
enable
range
reduction
polymerization
Despite
these
exciting
findings,
powerful
valuable
LBRs
would
expected,
given
structures
reactivities
easily
modulated,
provide
ample
opportunities
discover
new
this
Account,
summary
our
key
contributions
LBR-enabled
borylation
reactions
selective
activation
inert
carbon-heteroatom
bonds
will
presented.Organoboron
compounds
shown
versatile
chemical
society,
their
syntheses
rely
principally
ionic
The
development
mechanistically
different
allows
synthesizing
products
inaccessible
by
traditional
methods.
For
purpose,
we
progressively
developed
series
NHC-boryl
mediated
chemo-,
regio-,
stereoselective
alkenes
alkynes,
wide
variety
structurally
diverse
organoboron
molecules
successfully
prepared.
utility
borylated
also
demonstrated.
Furthermore,
disclosed
photoredox
protocol
for
oxidative
generation
enabled
useful
defluoroborylation
arylboration
reactions.Selective
bond
is
an
ideal
way
convert
simple
starting
materials
value-added
products,
while
cleavage
bonds,
particular
chemoselectivity
control
when
multiple
identical
present
similar
environments,
remains
long-standing
challenge.
We
envisaged
finely
tuning
properties
might
solution
address
Recently,
4-dimethylaminopyridine
(DMAP)-boryl
promoted
sequential
C-F
functionalization
trifluoroacetic
acid
derivatives,
α-C-F
selectively
snipped
via
spin-center
shift
mechanism.
This
strategy
enables
facile
conversion
abundantly
available
highly
mono-
difluorinated
molecules.
Encouraged
finding,
further
three-step
sequence
construct
all-carbon
quaternary
centers
from
trichloromethyl
groups,
where
three
C-Cl
cleaved
rational
choice
suitable
precursors
each
step.
dehydroxylative
alkylation
α-hydroxy
carboxylic
derivatives
achieved,
allowing
efficient
some
biomass
platform
value
products.
Chemical Communications,
Год журнала:
2024,
Номер
60(32), С. 4275 - 4289
Опубликована: Янв. 1, 2024
This
review
describes
the
recent
research
on
radical
hydroboration,
which
covers
different
boron
sources
including
N-heterocyclic
carbene
borane,
bis(pinacolato)diboron
and
pinacolborane,
as
well
strategies
in
boryl
generation.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 22, 2024
Abstract
A
protocol
for
trans
-hydroboration
of
indole
derivatives
using
heterogeneous
photocatalysis
with
NHC-borane
has
been
developed,
addressing
a
persistent
challenge
in
organic
synthesis.
The
protocol,
leveraging
high
crystalline
vacancy-engineered
polymeric
carbon
nitride
as
catalyst,
enables
diastereoselective
synthesis,
expanding
substrate
scope
and
complementing
existing
methods.
approach
emphasizes
eco-friendliness,
cost-effectiveness,
scalability,
making
it
suitable
industrial
applications,
particularly
renewable
energy
contexts.
catalyst’s
superior
performance,
attributed
to
its
rich
carbon-vacancies
well-ordered
structure,
surpasses
more
expensive
homogeneous
alternatives,
enhancing
viability
large-scale
use.
This
innovation
holds
promise
synthesizing
bioactive
compounds
materials
relevant
medicinal
chemistry
beyond.
Chemical Science,
Год журнала:
2023,
Номер
14(23), С. 6341 - 6347
Опубликована: Янв. 1, 2023
The
selective
difunctionalization
of
N-heterocyclic
carbene
(NHC)
boranes
with
alkenes
has
been
achieved
via
decatungstate
and
thiol
synergistic
catalysis.
catalytic
system
also
allows
stepwise
trifunctionalization,
leading
to
complex
NHC
three
different
functional
groups
which
are
challenging
prepare
by
other
methods.
strong
hydrogen-abstracting
ability
the
excited
enables
generation
boryl
radicals
from
mono-
di-substituted
for
realizing
borane
multifunctionalization.
This
proof-of-principle
research
provides
a
new
chance
fabricating
unsymmetrical
developing
boron-atom-economic
synthesis.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(2), С. 1296 - 1300
Опубликована: Янв. 4, 2024
Without
any
additives
and
photocatalysts,
the
visible-light-promoted
radical
cascade
reaction
between
alkynoates
phenyl
disulfides
has
been
developed
at
room
temperature.
Through
S–S
bond
photolysis
homolytic
cleavage,
addition
of
a
sulfur
radical,
aryl
migration,
decarboxylation,
H
atom
abstraction,
provides
an
efficient
practical
route
to
trisubstituted
1,1-diarylvinylsulfides
with
wide
scope
substrates
good
excellent
yields.
Molecules,
Год журнала:
2023,
Номер
28(2), С. 787 - 787
Опубликована: Янв. 12, 2023
In
recent
years,
the
importance
of
“environmentally
friendly
manufacturing”
has
been
increasing
toward
establishment
a
resource-recycling
society.
organic
synthesis,
as
well,
it
is
becoming
increasingly
important
to
develop
new
synthetic
strategies
with
resource
conservation
and
recycling
elemental
resources
in
mind,
rather
than
just
only
synthesis.
Many
studies
on
construction
frameworks
functional
molecules
using
ionic
reactions
transition-metal-catalyzed
have
reported,
but
most
them
focused
formation
carbon–carbon
bonds.
However,
essential
introduce
appropriate
groups
at
positions
order
for
express
their
functions,
furthermore,
highly
selective
preparation
multiple
considered
creation
molecules.
this
review,
we
focus
radical
high
group
selectivity
overview
progress
practical
methods
simultaneous
introduction
propose
future
that
emphasize
environmental
friendliness.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(22), С. 3824 - 3829
Опубликована: Сен. 23, 2023
Abstract
A
photo‐induced
metal‐free
radical
hydroboration
of
various
styrenes
with
NHC‐borane
has
been
developed,
which
can
provide
mono‐
and
di‐alkylated
boranes
in
a
selective
manner.
Besides,
this
strategy
also
be
applied
to
prepare
di‐functionalized
two
different
alkyl
groups.
Mild
reaction
conditions
good
functional
groups
compatibility
were
observed.
Preliminary
mechanism
for
was
proposed.
Green Chemistry,
Год журнала:
2023,
Номер
25(14), С. 5692 - 5697
Опубликована: Янв. 1, 2023
The
first
regio-reversed
domino
processes
of
triketone
enones
with
azlactones
are
established
leading
to
the
formation
a
variety
bicyclic
furofurans
bearing
vicinal
quaternary
carbons
in
good
excellent
yields.
