Angewandte Chemie,
Год журнала:
2023,
Номер
136(1)
Опубликована: Ноя. 21, 2023
Abstract
The
precise
control
of
the
regioselectivity
in
transition
metal‐catalyzed
migratory
hydrofunctionalization
alkenes
remains
a
big
challenge.
With
transient
ketimine
directing
group,
nickel‐catalyzed
β
‐selective
hydroarylation
and
hydroalkenylation
alkenyl
ketones
has
been
realized
with
aryl
boronic
acids
using
alkyl
halide
as
mild
hydride
source
for
first
time.
key
to
this
success
is
use
diphosphine
ligand,
which
capable
generation
Ni(II)‐H
species
presence
bromide,
enabling
efficient
insertion
alkene
into
sequent
rapid
chain
walking
process.
present
approach
diminishes
organosilanes
reductant,
tolerates
wide
array
complex
functionalities
excellent
regioselective
control.
Moreover,
catalytic
system
could
also
be
applied
azahetereoarenes,
thus
providing
general
preparation
1,2‐aryl
heteroaryl
motifs
potential
applications
pharmaceutical
discovery.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(9), С. 2946 - 2991
Опубликована: Янв. 1, 2023
This
review
discusses
the
applications
of
N-heterocyclic
carbene
ligands
and
their
influence
on
reactivity
selectivity
Ni-catalysed
alkene
functionalisations.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(46), С. 19294 - 19299
Опубликована: Ноя. 12, 2021
We
report
a
method
to
activate
α-3°
amines
for
deaminative
arylation
via
condensation
with
an
electron-rich
aldehyde
and
merge
this
reactivity
nickel
metallaphotoredox
generate
benzylic
quaternary
centers,
common
motif
in
pharmaceuticals
natural
products.
The
reaction
is
accelerated
by
added
ammonium
salts.
Evidence
provided
support
of
two
roles
the
additive:
inhibition
black
formation
acceleration
overall
rate.
demonstrate
robust
scope
amine
haloarene
coupling
partners
show
expedited
synthesis
ALK2
inhibitors.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Апрель 7, 2022
Abstract
Alkene
hydrocarbonation
reactions
have
been
developed
to
supplement
traditional
electrophile-nucleophile
cross-coupling
reactions.
The
branch-selective
hydroalkylation
method
applied
a
broad
range
of
unactivated
alkenes
remains
challenging.
Herein,
we
report
NiH-catalysed
proximal-selective
access
β-
or
γ-branched
alkyl
carboxylic
acids
and
β-,
γ-
δ-branched
amines.
A
iodides
bromides
with
different
functional
groups
can
be
installed
excellent
regiocontrol
availability
for
site-selective
late-stage
functionalization
biorelevant
molecules.
Under
modified
reaction
conditions
NiCl
2
(PPh
3
)
as
the
catalyst,
migratory
takes
place
provide
(rather
than
γ-)
branched
products.
keys
success
are
use
aminoquinoline
picolinamide
suitable
directing
combined
experimental
computational
studies
ligand
effects
on
regioselectivity
detailed
mechanisms.
ACS Catalysis,
Год журнала:
2022,
Номер
12(10), С. 5795 - 5805
Опубликована: Апрель 29, 2022
Direct
construction
of
fully
alkyl-substituted
tertiary
chiral
centers
remote
to
activating
groups
is
highly
challenging
and
desirable.
Herein,
a
Ni-catalyzed
enantioselective
hydroalkylation
unactivated
alkenes
with
alkyl
halides
at
room
temperature
reported,
providing
general
practical
access
stereogenic
carbon
not
adjacent
groups.
This
reaction
undergoes
the
regio-
stereoselective
hydrometalation
nontrivial
Markovnikov
selectivity,
followed
by
cross-coupling
electrophiles
trialkyl
saturated
The
mild
robust
conditions
enable
use
terminal
internal
primary
secondary
alkyl,
benzyl,
propargyl
construct
diverse
broad
functional
group
tolerance.
Moreover,
experimental
investigations
support
undergoing
irreversible
alkenes.
Density
theory
calculations
provide
further
insights
into
mechanism,
suggesting
migration
insertion
Ni(II)–H
species.
Finally,
origin
enantioselectivities
also
investigated.
ACS Catalysis,
Год журнала:
2022,
Номер
12(24), С. 14806 - 14811
Опубликована: Ноя. 22, 2022
We
report
a
conceptually
distinct
strategy
for
the
synthesis
of
1,1-diarylalkanes
and
triarylalkanes.
Key
to
this
approach
is
use
light
simultaneously
trigger
(i)
formation
CoIII–H
species
which
undergoes
H
atom
transfer
(MHAT)
styrenes,
giving
carbon-centered
radical,
(ii)
generation
persistent
(hetero)arene
radical.
Selective
coupling
these
two
yields
Markovnikov
hydroarylation
products
under
mild
conditions
without
precious
metals.
In
contrast
many
previous
approaches,
electron-deficient
partners
are
favored
it
possible
construct
highly
congested
quaternary
centers,
including
those
with
three
different
aryl
groups.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Сен. 7, 2023
Abstract
Selective
hydroarylation
of
dienes
has
potential
to
provide
swift
access
useful
building
blocks.
However,
most
existing
methods
rely
on
stabilised
by
an
aromatic
group
and
transmetallation
or
nucleophilic
attack
steps
require
electron‐rich
aryl
coupling
partners.
As
such,
there
are
few
examples
which
tolerate
wide‐spread
heteroarenes
such
as
pyridine.
Whilst
allylic
C−H
functionalisation
could
be
considered
alternative
approach,
the
positional
selectivity
unsymmetrical
substrates
is
hard
control.
Here,
we
report
a
general
approach
for
selective
hydropyridylation
under
mild
conditions
using
metal
catalysed
hydrogen‐atom
transfer.
Photoinduced,
reductive
enable
simultaneous
formation
cobalt‐hydride
catalyst
persistent
radical
easily‐synthesised
pyridyl
phosphonium
salts.
This
facilitates
in
traceless
manner
at
C4‐position
wide‐range
pyridine
substrates.
The
mildness
method
underscored
its
functional‐group
tolerance
demonstrated
applications
late‐stage
functionalisation.
Based
combination
experimental
computational
studies,
propose
mechanistic
pathway
proceeds
through
non‐reversible
transfer
(HAT)
from
cobalt
hydride
species
uniquely
presence
other
olefins
due
much
higher
relative
barrier
associated
with
olefin
HAT.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(51), С. 26511 - 26517
Опубликована: Окт. 15, 2021
Abstract
A
metallaphotoredox‐catalyzed
strategy
for
the
selective
and
divergent
aminocarbonylation
of
alkynes
with
amines
1
atm
CO
is
reported.
This
synergistic
protocol
not
only
enables
Markovnikov‐selective
hydroaminocarbonylation
to
afford
α,β‐unsaturated
amides,
but
also
facilitates
a
sequential
four‐component
hydroaminocarbonylation/radical
alkylation
in
presence
tertiary
secondary
alkyl
boronate
esters,
which
allows
straightforward
conversion
into
corresponding
amides.
Preliminary
mechanistic
studies
disclose
that
photoinduced
oxidative
insertion
aniline
nickel
followed
by
migratory
(carbamoyl)nickel
species
could
be
involved.
