Angewandte Chemie,
Год журнала:
2023,
Номер
135(46)
Опубликована: Сен. 29, 2023
Abstract
Catalytic
asymmetric
methods
for
the
synthesis
of
synthetically
versatile
P‐stereogenic
building
blocks
offer
an
efficient
and
practical
approach
diversity‐oriented
preparation
P‐chiral
phosphorus
compounds.
Herein,
we
report
first
nickel‐catalyzed
secondary
aminophosphine‐boranes
by
addition
primary
phosphines
to
azo
We
further
demonstrate
that
P−H
P−N
bonds
on
these
phosphanyl
hydrazine
can
be
reacted
sequentially
stereospecifically
access
various
compounds
with
structural
diversity.
A
second
generation
catalytic
two-phase
strategy
for
the
enantioselective
synthesis
of
chiral
at
P(V)
compounds
is
described.
This
protocol,
consisting
a
bifunctional
iminophosphorane
(BIMP)
catalyzed
nucleophilic
desymmetrization
prochiral,
bench
stable
precursors
and
subsequent
enantiospecific
substitution
allows
divergent
access
to
wide
range
C-,
N-,
O-
S-
substituted
containing
from
handful
enantioenriched
precursors.
new
catalyst/leaving
group
combination
allowed
far
wider
substrate
scope
increased
reaction
efficiency
practicality
over
previously
established
protocols.
The
resulting
intermediates
could
then
be
converted
an
even
greater
distinct
classes
by
displacement
remaining
leaving
as
well
allowing
further
diversification
downstream.
Density
functional
theory
(DFT)
calculations
were
performed
pinpoint
origin
enantioselectivity
BIMP-catalyzed
desymmetrization,
rationalize
how
superior
leads
generality
in
our
second-generation
system,
shed
light
onto
observed
retention
inversion
pathways
when
performing
late-stage
SN2@P
reactions
with
Grignard
reagents.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(46)
Опубликована: Сен. 29, 2023
Abstract
Catalytic
asymmetric
methods
for
the
synthesis
of
synthetically
versatile
P‐stereogenic
building
blocks
offer
an
efficient
and
practical
approach
diversity‐oriented
preparation
P‐chiral
phosphorus
compounds.
Herein,
we
report
first
nickel‐catalyzed
secondary
aminophosphine‐boranes
by
addition
primary
phosphines
to
azo
We
further
demonstrate
that
P−H
P−N
bonds
on
these
phosphanyl
hydrazine
can
be
reacted
sequentially
stereospecifically
access
various
compounds
with
structural
diversity.
