Amine-Borane-Mediated, Nickel/Photoredox-Catalyzed Cross-Electrophile Coupling between Alkyl and Aryl Bromides
Ke-Rong Li,
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Xian‐Chen He,
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Jie Gao
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et al.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(17), P. 12658 - 12667
Published: Aug. 19, 2024
Nickel/photoredox
catalysis
has
emerged
as
a
powerful
platform
for
exploring
nontraditional
and
challenging
cross-couplings.
Herein,
metallaphotoredox
catalytic
protocol
been
developed
on
the
basis
of
tertiary
amine-ligated
boryl
radical-induced
halogen
atom
transfer
process
under
blue-light
irradiation.
A
wide
variety
aryl
heteroaryl
bromides
featuring
different
functional
groups
pharmaceutical
moieties
were
facilely
coupled
to
rapidly
install
C(sp3)-enriched
aromatic
scaffolds.
The
compatibility
Lewis
base-ligated
borane
with
nickel
was
well
exemplified
extend
chemical
space
Ni-catalyzed
cross-electrophile
coupling.
Language: Английский
Visible light-induced halogen-atom transfer by N-heterocyclic carbene-ligated boryl radicals for diastereoselective C(sp3)–C(sp2) bond formation
Luca Capaldo,
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Ting Wan,
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Robin Mulder
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et al.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(36), P. 14844 - 14850
Published: Jan. 1, 2024
In
this
work,
we
report
the
synthesis
of
vinyl
chlorides
from
chloroalkynes
via
ligated
boryl
radicals-mediated
XAT
under
visible
light.
This
study
introduces
first
protocol
using
to
establish
a
C(sp
3
)–C(sp
2
)
bond
through
radical
addition.
Language: Английский
Controllable Hydrodebromination of Tribromomethyl Groups via Lewis Base–Borane-Mediated Ionic and Radical Pathways
Synthesis,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Abstract
Compounds
bearing
mono-
and
dibromomethyl
groups
are
extensively
utilized
in
synthetic
medicinal
chemistry.
In
this
regard,
selective
debromination
of
readily
or
easily
accessible
tribromomethyl
compounds
offers
a
direct
efficient
method
to
access
those
two
moieties.
work,
we
introduced
Lewis
base–borane-mediated
hydrodebromination
via
ionic
radical
pathway.
Using
4-(dimethylamino)pyridine–borane
(DMAP-BH3)
as
hydride
donor,
monohydrodebromination
was
achieved
nucleophilic
substitution
by
hydride,
delivering
groups.
On
the
other
hand,
treatment
with
an
N-heterocyclic
carbene–borane
(NHC-BH2CN)
boryl
precursor
presence
dilauroyl
peroxide
(DLP)
initiator
afforded
monobromomethyl
through
consecutive
bromine
atom
abstractions
cleave
C–Br
bonds.
Various
group
acetamides
acetates
were
applied
developed
protocol,
showcasing
good
functional
tolerance
broad
substrate
scope.
Language: Английский
Modular assembly of amines and diborons with photocatalysis enabled halogen atom transfer of organohalides for C(sp3)–C(sp3) bond formation
Rong‐Bin Liang,
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Tingting Miao,
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Xiang-Rui Li
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et al.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
new
photocatalytic
approach
by
using
the
assembly
of
DABCO
A1
and
B
2
Nep
B1
has
been
established
to
enable
cross-coupling
organohalides
alkenes
for
C(sp
3
)–C(sp
)
bond
formation.
Language: Английский
Photocatalytic Borylation of Imines and Alkenes via Decarboxylation of Trimethylamine Carboxyborane: A New Approach for Generating Boryl Radicals
Haowen Jiang,
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Hao-Ni Qin,
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Ai-Lian Wang
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et al.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(43), P. 9282 - 9287
Published: Oct. 23, 2024
In
this
study,
we
investigated
the
photocatalytic
decarboxylation
of
trimethylamine
carboxyborane
under
mild
conditions,
successfully
generating
boryl
radicals
for
subsequent
borylation
reactions
with
imines
and
various
alkenes.
This
method
exhibited
broad
substrate
compatibility,
including
functionalization
biologically
relevant
molecules.
Our
findings
expand
utility
beyond
its
role
as
a
carbon-monoxide-
drug-releasing
agent,
highlighting
potential
in
radical
chemistry
through
decarboxylation.
work
establishes
robust
foundation
further
exploration
synthetic
application
carboxyborane.
Language: Английский
Mechanistic Exploration of N-Heterocyclic Carbene Boranes as the Hydrogen Atom Transfer Reagent in Selective Hydrodefluorination Reactions
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 17547 - 17555
Published: Nov. 13, 2024
In
the
modern
era
of
organic
synthesis,
mechanisms
centered
on
radical
intermediates
have
become
increasingly
impactful.
Among
all
these,
hydrogen
atom
transfer
(HAT)
represents
one
most
fundamental
chemical
reaction
steps
and
has
found
applications
in
designing
practical
transformations.
Herein,
we
present
a
detailed
case
study
selective
hydrodefluorination
trifluoromethylarenes
utilizing
N-heterocyclic
carbene
boranes
(NHC-boranes)
as
donor.
Under
optimal
conditions
featuring
an
acridine-based
photocatalyst,
complete
selectivity
for
mono-hydrodefluorination
was
achieved
across
wide
array
substrates.
Comprehensive
mechanistic
studies
combining
experimental
computational
approaches
disproved
chain
process
involving
fluorine
but
rather
pointed
to
HAT
non-chain
mechanism,
where
key
step
involves
difluorobenzylic
abstracting
from
NHC-borane
generate
boryl
polarity-matched
fashion.
Evaluation
selection
Lewis
base-ligated
revealed
molecular
descriptors
critical
outcomes
this
reaction,
classification
model
built
explain
structure–reactivity
relationship
how
various
elementary
can
be
influenced.
These
results
collectively
provide
valuable
information
future
design
increase
utility
chemistry.
Language: Английский
Boryl Radical Mediated Hydro(gem-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes
Ruizeng Zhang,
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Hao Zhang,
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Pan Xu
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et al.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 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
Language: Английский
Quenching Rate Constants of Lewis Base‐Boryl Radical by Substrates: a Laser Flash Photolysis Study
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
31(8)
Published: Nov. 13, 2024
The
advanced
strategy
using
Lewis
base-boryl
radicals
(LBRs)
has
recently
been
proposed
for
the
addition
of
alkyl
substituents
to
full-carbon
quaternary
center
an
organic
molecule.
However,
as
rate-determining
step
in
whole
route,
reaction
rate
constants
LBRs
with
substrates
are
extremely
lacking.
In
this
paper,
4-dimethylaminopyridine
(DMAP)-BH2⋅
was
selected
a
representative
LBRs,
and
its
reactions
six
monochloro-substituted
substrates,
including
three
methyl
chlorobenzoates
chlorinated
acetanilides
were
studied
experiments
theoretical
calculations.
bimolecular
constants,
kq,
determined
laser
flash
photolysis
approach.
By
comparing
activation
energies
along
two
pathways,
we
have
clarified
attacking
carbonyl
oxygen
instead
chlorine
atom.
Furthermore,
noncovalent
interaction
(NCI)
analyses
on
these
indicate
that
weak
interactions,
such
hydrogen-bonding
van
der
Waals
significant
influence
reactivity
substrates.
Our
study
provides
concrete
clues
extend
synthetic
strategy.
Language: Английский