We
present
a
versatile
nickel-electrocatalytic
deaminative
cross-coupling
platform
for
the
efficient
construction
of
C(sp
3
)–C(sp
)
and
2
bonds
from
readily
available
alkyl
bistriflimides.
This
methodology
involves
assembly
two
leaving
groups
on
amines
to
form
bistriflimides,
followed
by
their
effective
coupling
with
wide
range
halides,
pseudohalides,
aryl
alkenyl
halides
under
electrochemical
reductive
conditions.
Moreover,
successful
application
relay
transition
metal–free
cross-electrophile
further
demonstrates
versatility
bistriflimides
as
valuable
building
blocks
in
organic
synthesis.
Combined
control
experiments
density
functional
theory
calculations
provide
insights
into
reaction
pathway
crucial
role
iodide
catalytic
process.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
ACS Catalysis,
Год журнала:
2022,
Номер
12(18), С. 11216 - 11225
Опубликована: Сен. 1, 2022
A
strategy
for
both
cross-electrophile
coupling
and
1,2-dicarbofunctionalization
of
olefins
has
been
developed.
Carbon-centered
radicals
are
generated
from
alkyl
bromides
by
merging
benzophenone
hydrogen
atom
transfer
(HAT)
photocatalysis
silyl
radical-induced
halogen
(XAT)
subsequently
intercepted
a
nickel
catalyst
to
forge
the
targeted
C(sp3)-C(sp2)
C(sp3)-C(sp3)
bonds.
The
mild
protocol
is
fast
scalable
using
flow
technology,
displays
broad
functional
group
tolerance,
amenable
wide
variety
medicinally
relevant
moieties.
Mechanistic
investigations
reveal
that
ketone
catalyst,
upon
photoexcitation,
responsible
direct
activation
silicon-based
XAT
reagent
(HAT-mediated
XAT)
furnishes
radical
ultimately
involved
in
turnover
catalytic
cycle.
Abstract
The
merging
of
photocatalysis
with
halogen‐atom
transfer
(XAT)
processes
has
proven
to
be
a
versatile
tool
for
the
generation
carbon‐centered
radicals
in
organic
synthesis.
XAT
are
unique
that
they
generate
without
requiring
use
strong
reductants
necessary
traditional
single
electron
(SET)
activation
halides.
Pathways
achieve
synthetic
applications
can
categorized
into
three
major
sections:
i)
heteroatom‐based
activators,
ii)
metal‐based
and
iii)
carbon‐based
activators
among
which
α‐aminoalkyl
have
taken
center
stage.
Access
these
as
reagents
gained
significant
attention
past
few
years
due
robustness
reactions,
simplicity
required,
broadness
their
applications.
Generation
is
simply
achieved
through
oxidation
tertiary
amines,
after
deprotonation
at
α‐position
generates
radicals.
Due
wide
scope
amines
available
tunable
nucleophilicity
radical
formed,
this
strategy
become
an
attractive
alternative
heteroatom/metal‐based
XAT.
In
minireview,
we
focus
our
on
recent
(2020–2023)
developments
uses
robust
technology
mediate
processes.
ACS Catalysis,
Год журнала:
2023,
Номер
13(13), С. 9018 - 9024
Опубликована: Июнь 22, 2023
Semiconductor
quantum
dots
(QDs)
offer
many
advantages
as
photocatalysts
for
synthetic
photoredox
catalysis,
but
no
reports
have
explored
the
use
of
QDs
with
nickel
catalysts
C-C
bond
formation.
We
show
here
that
5.7
nm
CdS
are
robust
photoredox-promoted
cross-electrophile
coupling
(40
000
TON).
These
conditions
can
be
utilized
on
small
scale
(96-well
plate)
or
adapted
to
flow.
NMR
studies
triethanolamine
(TEOA)
capped
active
catalyst
and
TEOA
displace
native
phosphonate
carboxylate
ligands,
demonstrating
importance
QD
surface
chemistry.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12658 - 12667
Опубликована: Авг. 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.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(3), С. 1703 - 1708
Опубликована: Янв. 16, 2024
Visible-light-induced
three-component
1,2-alkylpyridylation
of
alkenes
with
unactivated
alkyl
iodides
and
aryl
cyanides
is
reported
via
a
photocatalytic
halogen-atom
transfer
(XAT)
strategy.
This
metal-free
protocol
utilizes
readily
available
tertiary
alkylamine
as
the
terminal
reductant
to
smoothly
convert
into
corresponding
carbon
radical
species.
The
reaction
features
broad
substrate
scope,
excellent
functional
group
tolerance,
high
efficiency,
mild
conditions.
practicability
this
methodology
further
demonstrated
in
late-stage
difunctionalization
bioactive
molecules.
α-Amino
radicals
from
simple
tertiary
amines
were
employed
as
halogen
atom
transfer
(XAT)
agents
in
metallaphotoredox
catalysis
for
cross-electrophile
couplings
of
organic
bromides
with
iodides.
This
XAT
strategy
proved
to
be
efficient
the
generation
carbon
a
range
partners
(alkyl,
aryl,
alkenyl,
and
alkynyl
iodides).
The
reactivities
these
radical
intermediates
captured
by
nickel
organobromides
including
heteroaryl,
alkyl
bromides,
enabling
six
diverse
C-C
bond
formations.
Classic
named
reactions
Negishi,
Suzuki,
Heck,
Sonogashira
readily
achieved
net-reductive
fashion
under
mild
conditions.
More
importantly,
cross
coupling
was
viable
either
bromide
or
iodide
limiting
reactant
based
on
availability
substrates,
which
is
beneficial
late-stage
functionalization
complex
molecules.
scalability
this
method
batch
flow
investigated,
further
demonstrating
its
applicability.
Organic Letters,
Год журнала:
2022,
Номер
24(34), С. 6261 - 6265
Опубликована: Авг. 19, 2022
1,2-Dicarbofunctionalization
of
unactivated
olefin
has
been
reported
under
photoredox/nickel
dual
catalysis.
The
mildness
the
visible-light-mediated
reaction
allows
use
various
alkyl
and
aryl
electrophiles
with
several
sensitive
functional
groups.
protocol
was
equally
applied
for
late-stage
diversification
drugs
biologically
active
molecules.
Investigations
elucidated
importance
catalysis
α-amino-radical-mediated
halogen
atom
transfer
provided
us
nickel
complexes
involved
in
reaction.
