Green Synthesis and Catalysis,
Год журнала:
2022,
Номер
4(2), С. 124 - 134
Опубликована: Дек. 15, 2022
In
recent
years,
the
concept
of
transition
metal-catalyzed
functionalization
unsaturated
hydrocarbons
has
emerged
as
a
promising
strategy
for
developing
new
and
valuable
reactions,
attracted
considerable
attention
because
it
is
efficient
atomic
economical.
this
critical
review,
we
describe
advances
that
have
been
made
in
development
1,3-enynes
via
alkylene-π-allylpalladium
intermediates.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 3915 - 3925
Опубликована: Фев. 10, 2023
The
straightforward
construction
of
stereogenic
centers
bearing
unprotected
functional
groups,
as
in
nature,
has
been
a
persistent
pursuit
synthetic
chemistry.
Abundant
applications
free
enantioenriched
allyl
alcohol
and
hydroxylamine
motifs
have
made
the
asymmetric
hydration
hydroaminoxylation
conjugated
dienes
from
water
hydroxylamine,
respectively,
intriguing
efficient
routes
that
have,
however,
unachievable
thus
far.
A
fundamental
challenge
is
failure
to
realize
transition-metal-catalyzed
enantioselective
C–O
bond
constructions
via
hydrofunctionalization
dienes.
Here,
we
perform
comprehensive
study
toward
stereoselective
formal
by
synthesizing
set
new
P,N-ligands
identifying
an
aryl-derived
oxime
surrogate
for
both
hydroxylamine.
Asymmetric
hydroalkoxylation
with
also
elucidated.
Furthermore,
versatile
derivatizations
following
provide
indirect
but
concise
hydrophenoxylation,
hydrofluoroalkoxylation,
hydrocarboxylation
unreported
Finally,
ligand-to-ligand
hydrogen
transfer
process
proposed
based
on
results
preliminary
mechanistic
experiments.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(33)
Опубликована: Июнь 17, 2022
As
a
fundamental
and
synthetically
useful
C-C
bond
formation
reaction,
the
aldol
reaction
is
one
of
most
versatile
transformations
in
organic
synthesis.
However,
despite
extensive
research
on
asymmetric
versions
unified
method
for
stereoselective
access
to
complementary
syn
anti
diastereomeric
products
remains
be
developed.
In
this
study,
we
developed
synergistic
palladium/chiral
Lewis
base
system
that
overcomes
inherent
diastereoselectivity
bias
reactions
and,
as
result,
allowed
us
achieve
first
diastereodivergent
coupling
alkoxyallenes
with
pentafluorophenol
esters.
Computational
studies
suggest
mechanism
involving
an
intermolecular
protonative
hydropalladation
pathway
rather
than
palladium-hydride
migratory
insertion
pathway.
The
origin
stereochemistry
catalysis
rationalized
by
DFT
calculations.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(7), С. 2893 - 2898
Опубликована: Фев. 14, 2022
Transition-metal-catalyzed
branched
and
enantioselective
allylic
substitution
of
monosubstituted
precursors
with
carbon,
nitrogen,
oxygen,
sulfur,
fluoride
nucleophiles
has
been
well-established.
However,
such
a
selective
carbon–phosphorus
bond
formation
not
realized
probably
due
to
the
catalyst
deactivation
by
strong
coordinating
nature
phosphinylating
reagents.
Herein,
we
report
Rh-catalyzed
highly
regio-
synthesis
phosphine
oxides
in
presence
chiral
bisoxazoline-phosphine
ligand.
The
application
α-hydroxylalkylphosphine
keep
low
concentration
secondary
is
essential
for
high
yields.
addition
diphenyl
phosphoric
acid
was
found
only
activate
alcohols
but
also
accelerate
formation.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 25, 2022
Abstract
A
Cu/CPA
co‐catalytic
system
has
been
developed
for
achieving
the
direct
hydrophosphinylation
of
alkynes
with
phosphine
oxides
in
delivering
novel
axially
chiral
phosphorus‐containing
alkenes
high
yields
and
excellent
enantioselectivities
(up
to
99
%
yield
ee).
DFT
calculations
were
performed
elucidate
reaction
pathway
origin
enantiocontrol.
This
streamlined
modular
methodology
establishes
a
new
platform
design
application
styrene‐phosphine
ligands.
Green Chemistry,
Год журнала:
2023,
Номер
25(9), С. 3606 - 3614
Опубликована: Янв. 1, 2023
We
describe
a
cobalta-electro-catalyzed
enantioselective
C–H
annulation
of
arylphosphinamides
with
alkynes
for
P-stereogenic
compounds
via
desymmetrization
and
kinetic
resolution
processes.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(26)
Опубликована: Апрель 26, 2023
Transition
metal-catalyzed
hydrofunctionalization
of
methylenecyclopropanes
(MCPs)
has
presented
a
considerable
challenge
due
to
the
difficult
manipulation
regioselectivity
and
complicated
reaction
patterns.
Herein,
we
report
straightforward
Pd-catalyzed
ring-opening
hydrophosphinylation
MCPs
via
highly
selective
C-C
bond
cleavage.
This
method
allows
for
rapid
efficient
access
wide
range
chiral
allylic
phosphine
oxides
in
good
yields
high
enantioselectivities.
Additionally,
density
functional
theory
(DFT)
calculations
were
performed
elucidate
mechanism
origin
enantioselectivity.
Chemical Science,
Год журнала:
2023,
Номер
14(16), С. 4413 - 4417
Опубликована: Янв. 1, 2023
An
enantioselective
hydrophosphination
of
alkenyl
isoquinolines
is
developed
by
using
a
copper-chiral
diphosphine
ligand
catalyst.
It
provides
direct
and
atom-efficient
approach
to
prepare
variety
chiral
phosphines
with
an
isoquinoline
unit
in
good
yields
high
enantioselectivities.
In
addition,
these
phosphine
products
are
useful
bidentate
P,N-ligands
which
showed
potential
application
asymmetric
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июнь 19, 2023
We
describe
a
copper
catalyst
that
promotes
the
addition
of
phosphines
to
cyclopropenes
at
ambient
temperature.
A
range
cyclopropylphosphines
bearing
different
steric
and
electronic
properties
can
now
be
accessed
in
high
yields
enantioselectivities.
Enrichment
phosphorus
stereocenters
is
also
demonstrated
via
Dynamic
Kinetic
Asymmetric
Transformation
(DyKAT)
process.
combined
experimental
theoretical
mechanistic
study
supports
an
elementary
step
featuring
insertion
Cu
