Angewandte Chemie,
Год журнала:
2023,
Номер
135(44)
Опубликована: Сен. 18, 2023
Abstract
Enamides,
functional
derivatives
of
enamines,
play
a
significant
role
as
synthetic
targets.
However,
the
stereoselective
synthesis
these
molecules
has
posed
longstanding
challenge
in
organic
chemistry,
particularly
for
acyclic
enamides
that
are
less
thermodynamically
stable.
In
this
study,
we
present
general
strategy
constructing
β‐borylenamides
by
C−H
borylation,
which
provides
versatile
platform
generating
stereodefined
enamides.
Our
approach
involves
utilization
metalloid
borenium
cation,
generated
through
reaction
BBr
3
and
presence
two
different
additives,
avoiding
any
exogenous
catalyst.
Importantly,
stereoconvergent
nature
methodology
allows
use
starting
materials
with
mixed
E/Z
configurations,
thus
highlighting
unique
advantage
chemistry.
Mechanistic
investigations
have
shed
light
on
pivotal
roles
played
reactive
boron
species,
phenomenon
stereoconvergence.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(44)
Опубликована: Сен. 18, 2023
Enamides,
functional
derivatives
of
enamines,
play
a
significant
role
as
synthetic
targets.
However,
the
stereoselective
synthesis
these
molecules
has
posed
longstanding
challenge
in
organic
chemistry,
particularly
for
acyclic
enamides
that
are
less
thermodynamically
stable.
In
this
study,
we
present
general
strategy
constructing
β-borylenamides
by
C-H
borylation,
which
provides
versatile
platform
generating
stereodefined
enamides.
Our
approach
involves
utilization
metalloid
borenium
cation,
generated
through
reaction
BBr3
and
presence
two
different
additives,
avoiding
any
exogenous
catalyst.
Importantly,
stereoconvergent
nature
methodology
allows
use
starting
materials
with
mixed
E/Z
configurations,
thus
highlighting
unique
advantage
chemistry.
Mechanistic
investigations
have
shed
light
on
pivotal
roles
played
reactive
boron
species,
phenomenon
stereoconvergence.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(10)
Опубликована: Ноя. 16, 2022
An
efficient
regioselective
functionalization
of
2-aryl-heteroarenes
and
aryl
aldehydes
via
an
azaaryl
BF2
complex
has
been
developed.
Mechanistically
the
reaction
comprises
fluoride
to
bromide
ligand
exchange
on
boron
species
consecutive
C-B
bond
cleavage
deliver
a
broad
range
functionalized
products.
The
is
high
yielding,
substrate
scope
where
several
different
heteroarenes
can
be
with
chloro,
bromo,
iodo,
hydroxyl,
amine
in
highly
fashion.
method
applied
for
late-stage
or
rapid
skeleton
remodeling
instance
cross-couplings.
Organic Letters,
Год журнала:
2023,
Номер
25(31), С. 5875 - 5879
Опубликована: Июль 27, 2023
C–H
borylation
is
one
of
the
powerful
bond
functionalization
reactions.
In
this
context,
a
metal-free
benzophenones
using
hydrazone
as
traceless
directing
group
has
been
reported.
The
dibromoboron
intermediates
can
be
obtained
in
excellent
yields,
and
corresponding
arylboronic
esters
are
generated
moderate
to
yields.
Furthermore,
borylated
compounds
transformed
one-pot
method,
avoiding
loss
overall
yield
caused
by
separation
esters.
The Chemical Record,
Год журнала:
2023,
Номер
23(4)
Опубликована: Фев. 27, 2023
Abstract
Aromatic
organoboron
compounds
are
highly
valuable
building
blocks
in
organic
chemistry.
They
were
mainly
synthesized
through
aromatic
C−H
and
C−Het
borylation,
which
transition
metal‐catalysis
dominate.
In
the
past
decade,
with
increasing
attention
to
sustainable
chemistry,
numerous
metal‐free
borylation
transformations
have
been
developed
emerged
as
efficient
methods
towards
synthesis
of
compounds.
This
account
focuses
on
recent
advances
C−H,
C−N,
C−S,
C−O
provides
insights
where
further
developments
required.
Organic Letters,
Год журнала:
2024,
Номер
26(18), С. 3709 - 3714
Опубликована: Май 1, 2024
A
BBr3-mediated
S-directed
ortho
C–H
borylation
of
thiobenzamides
was
developed.
variety
ortho-borylated
were
obtained
in
moderate
to
good
yields
with
a
wide
functional
group
tolerance
under
simple
and
metal-free
conditions.
This
transformation
provided
convenient
practical
route
important
functionalized
thiobenzamides.
Organic Letters,
Год журнала:
2024,
Номер
26(22), С. 4631 - 4636
Опубликована: Май 23, 2024
A
novel
metal-free
chemoselective
C–H
hydroxylation
and
borylation
of
N-phenylbenzamides
using
BBr3
is
described.
The
protocol
generates
the
corresponding
phenols
arylboronic
esters
in
moderate
to
excellent
yields
under
mild
conditions
with
brilliant
chemoselectivity.
Additionally,
this
strategy
can
be
realized
one
pot,
several
potential
bioactive
derivatives
synthesized
efficiently.
Density
functional
theory
calculations
certify
that
preferred
pathway
for
process
formation
a
five-membered
boracycle.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(39)
Опубликована: Авг. 3, 2023
The
borylation
of
Csp3
-H
bonds
is
a
challenging
transformation
that
typically
restricted
to
transition
metal
catalysis.
Herein,
we
report
the
site-selective
metal-free
saturated
cyclic
amines.
It
possible
selectively
borylate
piperidine
derivatives
at
α
or
β
positions
according
reaction
conditions.
mechanism
was
supported
by
NMR
spectroscopy,
calorimetry
experiments
and
density
functional
theory
(DFT)
computations.
suggests
dehydrogenated
complexation
with
BBr3
produce
an
enamine
intermediate,
which
in
turn
borylated
either
position
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4249 - 4257
Опубликована: Янв. 1, 2024
The
Fe(OTf)
3
-promoted
directing
group-controlled
regioselective
C–H
borylation
of
2-arylarenolic
compounds
was
achieved
at
room
temperature,
affording
two
useful
arylboronic
acids
efficiently.
We
have
developed
a
BBr3-mediated,
metal-free
ortho
C-H
borylation
of
benzamides,
enabling
the
synthesis
wide
range
ortho-borylated
benzamides
in
moderate
to
good
yields.
This
transformation
offers
convenient
strategy
for
accessing
functionalized
which
are
valuable
intermediates
pharmaceuticals,
agrochemicals,
and
fine
chemical
synthesis.
