Organic Letters,
Год журнала:
2019,
Номер
21(20), С. 8454 - 8458
Опубликована: Окт. 10, 2019
A
first
example
of
radical
hydroboration
and
hydrosilylation
gem-difluoroalkenes
using
ABIN
as
the
initiator
is
described.
This
protocol
features
good
functional
group
tolerance,
operational
simplicity,
high
atom
economy,
easy
scale-up,
enabling
efficient
assembly
a
wide
range
α-difluorinated
alkylborons
alkylsilanes
in
moderate
to
excellent
yields.
The
synthetic
utility
these
products
demonstrated
by
further
transformation
C–B
bond
C–Si
into
valuable
CF2-containing
molecules.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
145(2), С. 991 - 999
Опубликована: Дек. 30, 2022
Herein,
we
present
a
comprehensive
study
on
the
use
of
N-heterocyclic
carbene
(NHC)-ligated
boryl
radicals
to
enable
C(sp3)–C(sp3)
bond
formation
under
visible-light
irradiation
via
Halogen-Atom
Transfer
(XAT).
The
methodology
relies
an
acridinium
dye
generate
boron-centered
from
corresponding
NHC-ligated
boranes
single-electron
transfer
(SET)
and
deprotonation.
These
subsequently
engage
with
alkyl
halides
in
XAT
step,
delivering
desired
nucleophilic
radicals.
strategy
is
very
mild
accommodates
broad
scope
halides,
including
medicinally
relevant
compounds
biologically
active
molecules.
key
role
operative
reaction
mechanism
has
been
elucidated
through
combination
experimental,
spectroscopic,
computational
studies.
This
stands
as
significant
advancement
chemistry
radicals,
which
had
long
restricted
radical
reductions,
enabling
C–C
photoredox
conditions.
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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 22874 - 22880
Опубликована: Авг. 2, 2024
A
novel
reactivity
toward
C-F
bond
functionalization
has
been
developed,
which
could
be
designated
as
fluorine
atom
transfer
(FAT).
photoexcited
state
of
an
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(31), С. 12817 - 12821
Опубликована: Апрель 27, 2020
In
this
Communication,
we
report
an
unprecedented
β-regioselective
radical
inverse
hydroboration
(compared
with
ionic
hydroboration)
of
α,β-unsaturated
amides
NHC-BH3
enabled
by
photoredox
catalysis.
Density
functional
theory
(DFT)
calculations
show
that
the
unique
cycle
is
a
key
factor
to
control
hydroboration,
lowering
energy
barrier
in
comparison
other
pathways.
This
protocol
provides
general
and
convenient
route
construct
wide
range
structurally
diverse
β-borylated
synthetically
useful
yields
under
mild
conditions.
Organic Letters,
Год журнала:
2020,
Номер
22(5), С. 1742 - 1747
Опубликована: Фев. 13, 2020
The
first
photoredox-catalyzed
defluoroborylation
of
polyfluoroarenes
with
NHC-BH3
has
been
facilely
achieved
at
room
temperature
via
a
single-electron-transfer
(SET)/radical
addition
pathway.
This
new
strategy
makes
full
use
the
advantage
photoredox
catalysis
to
generate
key
boryl
radical
direct
activation
B-H
bond.
Good
functional
group
tolerance
and
high
regioselectivity
offer
this
protocol
incomparable
advantages
in
preparing
wide
array
valuable
polyfluoroarylboron
compounds.
Moreover,
both
computational
experimental
studies
were
performed
illustrate
reaction
mechanism.
Organic Letters,
Год журнала:
2021,
Номер
23(5), С. 1891 - 1897
Опубликована: Фев. 16, 2021
Borylated
aza-arenes
are
of
great
importance
in
the
area
organic
synthesis.
A
radical
borylative
cyclization
isocyanoarenes
with
N-heterocyclic
carbene
borane
(NHC-BH3)
under
metal-free
conditions
was
developed.
The
reaction
allows
efficient
assembly
several
types
borylated
(phenanthridines,
benzothiazoles,
etc.),
which
difficult
to
access
using
alternative
methods.
Mild
conditions,
a
good
functional-group
tolerance,
and
generally
efficiencies
were
observed.
utility
these
products
is
demonstrated,
mechanism
discussed.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(66)
Опубликована: Сен. 6, 2022
Abstract
The
electrochemical
synthesis
of
fluorinated
allyl
silanes
and
boronates
was
disclosed.
addition
electrogenerated
boryl
or
silyl
radicals
onto
many
α‐trifluoromethyl
α‐difluoromethylstyrenes
in
an
undivided
cell
allowed
the
formation
a
large
panel
synthetically
useful
gem
‐difluoro
γ‐fluoroallyl
(64
examples,
from
31
%
to
95
yield).
In
addition,
scale
up
reactions
under
continuous
flow
showcased
using
reactor
with
promising
volumetric
productivity
(688
g.L
−1
.h
496
).
Moreover,
synthetic
utility
these
building
blocks
highlighted
through
versatile
transformations.
Finally,
plausible
reaction
mechanisms
were
suggested
explain
products.
Organic Letters,
Год журнала:
2022,
Номер
24(40), С. 7372 - 7377
Опубликована: Сен. 29, 2022
Herein,
a
B2pin2-mediated
radical
cascade
cyclization/aromatization
reaction
of
enaminone
with
pyridine
is
described.
This
strategy
provides
practical
way
for
the
construction
valuable
functionalized
indolizines
under
metal-,
external
oxidant-,
and
base-free
conditions,
which
could
be
compatible
various
kinds
functional
groups,
such
as
halogen,
π-system,
heterocycle,
ferrocenyl,
etc.
A
preliminary
mechanism
investigation
indicated
that
pyridine-boryl
formed
in
situ
triggered
to
occur.
