Nickel
demonstrates
excellent
performance
in
C-C
or
C-X
cross-coupling
reactions
involving
a
SET
process.
However,
the
Ni(I)/Ni(III)
two-electron
pathway,
which
does
not
require
light
irradiation,
is
still
rare,
particularly
asym-metric
version.
Here,
we
disclose
Ni(II)-catalyzed
asymmetric
C-P
reaction
via
redox
pathway.
Combined
experimental
and
computational
research
reveals
that
Ni(II)
can
be
readily
reduced
to
Ni(0)
by
secondary
phosphine
oxides,
resulting
formation
of
Ni(I)
active
catalyst
through
comproportiona-tion.
The
discovery
mechanism
may
serve
as
new
paradigm
Ni
catalysis,
offering
exciting
opportunities
complementary
traditional
Coordination Chemistry Reviews,
Год журнала:
2023,
Номер
489, С. 215192 - 215192
Опубликована: Май 9, 2023
Since
the
development
of
BisP*
ligand
by
Imamoto,
P-stereogenic
phosphines
bearing
a
bulky
tert-butyl
group
and
smaller
alkyl
have
demonstrated
extraordinary
proficiency
in
wide
range
asymmetric
processes.
Over
time,
this
class
ligands
has
brought
about
introduction
more
rigid
backbones,
three-hindered
quadrant
concept,
substitution
adamantyl.
The
methyl
fragment
also
been
introduced
phosphino-oxazoline-type
ligands,
chemists
industrial
sector
contributed
to
evolution
reporting
first
successful
Buchwald-type
monophosphines
for
coupling
reactions.
present
review
covers
synthesis
applications
that
developed
since
advent
late
1990s,
with
special
emphasis
on
successfully
applied
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(15)
Опубликована: Фев. 14, 2023
Abstract
A
general
and
mild
nickel‐catalyzed
enantioselective
C(sp
2
)−P
cross‐coupling
for
synthesizing
P‐stereogenic
phosphine
oxides
has
been
developed.
The
asymmetric
alkenylation/arylation
of
racemic
secondary
with
alkenyl/aryl
bromides
generated
high
yields
enantioselectivities.
Various
functional
groups
were
tolerated,
the
applications
this
method
demonstrated
through
late‐stage
functionalization
product
transformations.
Organic Letters,
Год журнала:
2023,
Номер
25(5), С. 816 - 820
Опубликована: Янв. 24, 2023
The
reductive
cleavage
of
C(Ar)-X
bonds
is
the
key
step
for
cross
coupling
Ar-X
with
other
groups.
In
this
work,
under
irradiation
407
nm
LEDs
using
sodium
formate
as
reductant
and
thiol
hydrogen
atom
transfer
agent,
a
variety
(hetero)aryl
chlorides,
bromides,
iodides
could
be
reduced
to
corresponding
(hetero)arenes.
intermediates,
aryl
radicals,
trapped
by
either
hydrogen,
phosphite,
or
borates.
same
reduction
conditions
can
extended
deprotection
sulfonamides.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(18)
Опубликована: Фев. 21, 2024
A
broadly
improved
second
generation
catalytic
two-phase
strategy
for
the
enantioselective
synthesis
of
stereogenic
at
phosphorus
(V)
compounds
is
described.
This
protocol,
consisting
a
bifunctional
iminophosphorane
(BIMP)
catalyzed
nucleophilic
desymmetrization
prochiral,
bench
stable
P(V)
precursors
and
subsequent
enantiospecific
substitution
allows
divergent
access
to
wide
range
C-,
N-,
O-
S-
substituted
containing
from
handful
enantioenriched
intermediates.
new
ureidopeptide
BIMP
catalyst/thiaziolidinone
leaving
group
combination
allowed
far
wider
substrate
scope
increased
reaction
efficiency
practicality
over
previously
established
protocols.
The
resulting
intermediates
could
then
be
transformed
into
an
even
greater
distinct
classes
by
displacement
remaining
as
well
allowing
further
diversification
downstream.
Density
functional
theory
(DFT)
calculations
were
performed
pinpoint
origin
enantioselectivity
BIMP-catalyzed
desymmetrization,
rationalize
how
superior
catalyst/leaving
leads
generality
in
our
second-generation
system,
shed
light
onto
observed
stereochemical
retention
inversion
pathways
when
performing
late-stage
S
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(45), С. 8818 - 8832
Опубликована: Янв. 1, 2022
Photochemical
C–P
bond
cross-coupling
in
aromatics
via
C–X
(X
=
F,
Cl,
Br,
I),
C–N
and
C–O
cleavages
with/without
photosensitizer
were
summarized
this
review.
Organic Letters,
Год журнала:
2023,
Номер
25(33), С. 6139 - 6142
Опубликована: Авг. 11, 2023
Nickel
performs
excellently
in
C–C
and
C–X
cross-coupling
reactions.
Here,
we
disclose
a
Ni(II)-catalyzed
asymmetric
C–P
reaction
to
afford
valuable
chiral
heterocyclic
tertiary
phosphine
oxides.
The
method
is
mild
efficient,
which
invokes
self-sustained
nickel
catalytic
cycle
without
an
external
reductant,
light
irradiation,
or
electricity.
Chemistry Letters,
Год журнала:
2023,
Номер
52(9), С. 703 - 714
Опубликована: Июль 31, 2023
Abstract
Novel
synthetic
methods
for
P-chirogenic
four-coordinate
pentadentate
organophosphorus
compounds
are
described.
The
pathways
commenced
with
the
use
of
phosphates
bearing
a
binaphthyl
group
and
their
congeners.
These
underwent
reactions
fluoride
ion,
metal
hydroxides,
alkoxides,
Grignard
reagents,
resulting
in
transfer
axial
chirality
from
to
central
phosphorus
atom.
As
result,
products
incorporating
were
obtained.
substitution
these
newly
formed
alkoxides
reagents
led
formation
phosphates,
phosphonates,
phosphinates,
some
sulfur
isologues.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(6), С. 1963 - 1963
Опубликована: Янв. 1, 2023
Enantioenriched
organophosphates
are
ubiquitous
in
a
large
array
of
chiral
ligands,
catalysts
and
bioactive
molecules.Over
the
past
few
decades,
synthetic
chemists
have
contributed
substantial
efforts
to
develop
efficient
methodologies
for
construction
P-chiral
phosphine
derivatives,
considerably
enriching
arsenal
organophosphine
ligands
promising
pharmaceutical
molecules.Among
them,
number
works
focused
on
synthesis
oxides
because
it
is
more
stability
than
trivalent
phosphines
convenient
reduction.In
view
rapid
progress
this
area
currently
available
reviews,
last
three
years
summarized
discussed,
namely
from
2020
2022.The
description
strategy
divided
into
five
segments,
involving
asymmetric
induction,
catalytic
desymmetrization,
synthesis,
kinetic
resolution
or
dynamic
transformation,
enzyme
catalysis.
