Dinuclear gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 2, 2024
The
enormous
and
widespread
use
of
organoboronic
acids
has
prompted
the
development
innovative
synthetic
methodologies
to
meet
demands
on
structural
diversity
functional
group
tolerance.
existing
photoinduced
defunctionalization
radical
borylation,
typically
focused
conversion
one
C-X
bond
(X=
Br,
I,
or
other
leaving
group)
into
only
C-B
bond.
Herein,
we
disclose
a
divergent
dechloroborylation
reaction
enabled
by
dinuclear
gold
catalysis
with
visible
light
irradiation.
A
wide
range
structurally
diverse
alkyl
boronic,
α-chloroboronic,
gem-diboronic
esters
can
be
synthesized
in
moderate
good
yields
(up
92%).
Its
robustness
is
further
demonstrated
preparative
scale
applied
late-stage
diversification
complex
molecules.
process
hinges
C-Cl
relay
activation
readily
available
gem-dichloroalkanes
through
inner-sphere
electron
transfer,
overcoming
redox
potential
limits
unreactive
chlorides.
Язык: Английский
Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters**
Alessandro Marotta,
Fang Hao,
Callum E. Adams
и другие.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июнь 16, 2023
Abstract
Operationally
simple
strategies
to
assemble
boron
containing
organic
frameworks
are
highly
enabling
in
synthesis.
While
conventional
retrosynthetic
logic
has
engendered
many
platforms
focusing
on
the
direct
formation
of
C−B
bonds,
α‐boryl
radicals
have
recently
reemerged
as
versatile
open‐shell
alternatives
access
organoborons
via
adjacent
C−C
bond
formation.
Direct
light‐enabled
α‐activation
is
currently
contingent
photo‐
or
transition
metal‐catalysis
activation
efficiently
generate
radical
species.
Here,
we
disclose
a
facile
α‐halo
boronic
esters
using
only
visible
light
and
Lewis
base
enable
homolytic
scission.
Intermolecular
addition
styrenes
facilitates
rapid
construction
E
‐allylic
esters.
The
simplicity
permits
strategic
merger
this
construct
with
selective
energy
transfer
catalysis
complimentary
stereodivergent
synthesis
Z
Язык: Английский
Simultaneous Stereoinvertive and Stereoselective C(sp3)–C(sp3) Cross-Coupling of Boronic Esters and Allylic Carbonates
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(20), С. 13719 - 13726
Опубликована: Май 9, 2024
With
increasing
interest
in
constructing
more
three-dimensional
entities,
there
has
been
growing
cross-coupling
reactions
that
forge
C(sp3)–C(sp3)
bonds,
which
leads
to
additional
challenges
as
it
is
not
just
a
difficult
bond
construct
but
issues
of
stereocontrol
also
arise.
Herein,
we
report
the
stereocontrolled
enantioenriched
boronic
esters
with
racemic
allylic
carbonates
enabled
by
iridium
catalysis,
leading
formation
bonds
single
or
vicinal
stereogenic
centers.
The
method
shows
broad
substrate
scope,
enabling
primary,
secondary,
and
even
tertiary
be
employed,
can
used
prepare
any
four
possible
stereoisomers
coupled
product
chiral
new
method,
combines
simultaneous
enantiospecific
reaction
nucleophile
enantioselective
electrophile
process,
offers
solution
for
stereodivergent
two
C(sp3)
fragments.
Язык: Английский
Mechanochemical Synthesis of α‐halo Alkylboronic Esters
Advanced Science,
Год журнала:
2024,
Номер
11(33)
Опубликована: Июль 3, 2024
α-halo
alkylboronic
esters,
acting
as
ambiphilic
synthons,
play
a
pivotal
role
versatile
intermediates
in
fields
like
pharmaceutical
science
and
organic
chemistry.
The
sequential
transformation
of
carbon-boron
carbon-halogen
bonds
into
broad
range
carbon-X
allows
for
programmable
bond
formation,
facilitating
the
incorporation
multiple
substituents
at
single
position
streamlining
synthesis
complex
molecules.
Nevertheless,
synthetic
potential
these
compounds
is
constrained
by
limited
reaction
patterns.
Additionally,
conventional
methods
often
necessitate
use
bulk
toxic
solvents,
exhibit
sensitivity
to
air/moisture,
rely
on
expensive
metal
catalysts,
involve
extended
times.
In
this
report,
ball
milling
technique
introduced
that
overcomes
limitations,
enabling
external
catalyst-free
multicomponent
coupling
aryl
diazonium
salts,
alkenes,
simple
halides.
This
approach
offers
general
straightforward
method
obtaining
diverse
array
thereby
paving
way
extensive
utilization
synthons
fine
chemicals.
Язык: Английский
Construction of α-Halogenated Boronic Esters via Visible Light-Induced C–H Bromination
Feng‐Chen Gao,
Ming Li,
Heng-Yu Gu
и другие.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(19), С. 14246 - 14254
Опубликована: Сен. 21, 2023
α-Halogenated
boronic
esters
are
versatile
building
blocks
that
can
be
diversified
into
a
wide
variety
of
polyfunctionalized
molecules.
However,
their
synthetic
potential
has
been
hampered
by
limited
preparation
methods.
Herein,
we
report
visible
light-induced
C-H
bromination
reaction
readily
available
benzyl
esters.
This
method
features
high
yields,
mild
conditions,
simple
operation,
and
good
functional
group
tolerance.
The
analogous
chlorides
iodides
accessed
via
Finkelstein
reaction.
Synthesis
halogenated
geminal
diborons
also
demonstrated.
Язык: Английский
Oxidation of Carbon–Boron Bonds
Elsevier eBooks,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Язык: Английский
Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters**
Alessandro Marotta,
Fang Hao,
Callum E. Adams
и другие.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(34)
Опубликована: Июнь 16, 2023
Abstract
Operationally
simple
strategies
to
assemble
boron
containing
organic
frameworks
are
highly
enabling
in
synthesis.
While
conventional
retrosynthetic
logic
has
engendered
many
platforms
focusing
on
the
direct
formation
of
C−B
bonds,
α‐boryl
radicals
have
recently
reemerged
as
versatile
open‐shell
alternatives
access
organoborons
via
adjacent
C−C
bond
formation.
Direct
light‐enabled
α‐activation
is
currently
contingent
photo‐
or
transition
metal‐catalysis
activation
efficiently
generate
radical
species.
Here,
we
disclose
a
facile
α‐halo
boronic
esters
using
only
visible
light
and
Lewis
base
enable
homolytic
scission.
Intermolecular
addition
styrenes
facilitates
rapid
construction
E
‐allylic
esters.
The
simplicity
permits
strategic
merger
this
construct
with
selective
energy
transfer
catalysis
complimentary
stereodivergent
synthesis
Z
Язык: Английский
Fe(0)-catalyzed radical halosulfonation: Regioselective synthesis of α-halo alkylboronic esters
Molecular Catalysis,
Год журнала:
2024,
Номер
557, С. 113954 - 113954
Опубликована: Фев. 24, 2024
Язык: Английский
Boryl Radical Mediated Hydro(gem-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 9, 2024
NHC
boryl
radical
mediated
halogen
atom
transfer
(XAT)
is
useful
in
organic
synthesis.
Yet,
most
of
the
reaction
ends
only
with
reducing
to
hydrogen,
that
is,
C-X
C-H.
This
especially
dominant
for
electron-deficient
alkyl
halides,
where
formed
electrophilic
reacts
rapidly
boranes.
Herein,
by
employing
a
sterically
hindered
borane
as
precursor
(IPr·BH
Язык: Английский