Angewandte Chemie,
Год журнала:
2023,
Номер
136(7)
Опубликована: Дек. 22, 2023
Abstract
This
paper
presents
a
Mn(I)‐catalysed
methodology
for
the
enantioselective
hydrophosphination
of
terminal
alkenyl
aza‐heteroarenes.
The
catalyst
operates
through
H−P
bond
activation,
enabling
successful
diverse
range
alkenyl‐heteroarenes
with
high
enantioselectivity.
presented
protocol
addresses
inherently
low
reactivity
and
commonly
encountered
suboptimal
enantioselectivities
these
challenging
substrates.
As
an
important
application
we
show
that
this
method
facilitates
synthesis
non‐symmetric
tridentate
P,N,P‐containing
ligand
like
structure
in
just
two
synthetic
steps
using
single
catalytic
system.
Chemical Reviews,
Год журнала:
2024,
Номер
124(14), С. 8657 - 8739
Опубликована: Июль 2, 2024
Chiral
phosphorus
ligands
play
a
crucial
role
in
asymmetric
catalysis
for
the
efficient
synthesis
of
useful
optically
active
compounds.
They
are
largely
categorized
into
two
classes:
backbone
chirality
and
P-stereogenic
ligands.
Most
reported
belong
to
former
class.
Privileged
ones
such
as
BINAP
DuPhos
frequently
employed
wide
range
catalytic
transformations.
In
contrast,
latter
class
has
remained
small
family
many
years
mainly
because
their
synthetic
difficulty.
The
late
1990s
saw
emergence
novel
with
superior
enantioinduction
ability
Rh-catalyzed
hydrogenation
reactions.
Since
then,
numerous
have
been
synthesized
used
This
Review
summarizes
thus
far,
including
stereochemical
electronic
properties
that
afford
high
excellent
enantioselectivities.
Examples
reactions
use
this
described
together
applications
construction
key
intermediates
natural
products
therapeutic
agents.
literature
covered
dates
back
1968
up
until
December
2023,
centering
on
studies
published
later
years.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(45), С. 31339 - 31347
Опубликована: Ноя. 4, 2024
Nucleoside
analogues
have
seen
significant
advancements
in
treating
viral
infections
and
cancer
through
ProTide
technology,
leading
to
a
series
of
FDA-approved
drugs
such
as
sofosbuvir,
tenofovir
alafenamide,
remdesivir.
The
stereochemical
configuration
at
the
phosphorus
center
ProTides
significantly
influences
their
pharmacological
properties,
necessitating
efficient
stereoselective
synthesis.
Traditional
methods
using
chiral
auxiliaries
or
nonracemic
phosphorylating
agents
are
labor-intensive
inefficient,
while
recent
organocatalytic
approaches,
despite
promise,
still
face
limitations.
Herein,
we
present
novel
approach
employing
metal
complexes
for
assembly
P-stereogenic
via
asymmetric
P-O
bond
formation.
This
leverages
catalyst
activate
electrophilic
reagent,
facilitating
base-promoted
nucleophilic
replacement
pathway.
Our
protocol,
featuring
mild
reaction
conditions
broad
applicability,
enables
highly
synthesis
previously
inaccessible
(
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 6188 - 6193
Опубликована: Апрель 8, 2024
Enantioselective
reduction
of
cyclopropenyl
esters
and
ketones
to
optically
active
cyclopropanes
has
been
achieved
by
using
whole-cell-overexpressing
ene-reductases
(EREDs).
By
these
enzymes,
trans-cyclopropanes
were
isolated
in
good
yield
high
enantiomeric
excess.
A
wide
range
cyclopropane
obtained,
a
variety
substituent
patterns
on
the
cyclopropenes
tolerated.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 29, 2024
Catalytic
asymmetric
synthesis
of
polysubstituted
chiral
cyclopropane
presents
a
significant
challenge
in
organic
due
to
the
difficulty
enantioselective
control.
Here
we
report
rhodium-catalyzed
highly
chemo-,
regio-
and
hydroformylation
trisubstituted
cyclopropenes
affording
quaternary
cyclopropanes.
Importantly,
easy
made
sterically
bulky
ligand
L1
can
effectively
suppress
hydrogenation
decomposition
reactions
give
cyclopropanes
with
high
enantioselectivities
for
both
aryl
alkyl
functionalized
substrates.
Control
experiments
computational
studies
reveal
hindered
well-defined
pocket
instead
substrates
bearing
electron-withdrawing
diester
groups
is
important
controlling
enantioselectivity
regioselectivity.
Scale-up
reaction
follow-up
diverse
transformations
are
also
presented.
Density
Functional
theory
(DFT)
computations
suggest
that
enantio-selectivities
originate
from
cyclopropene
insertion
Rh-H
bond.
The
regioselectivity
found
benefit
presence
more
efficient
noncovalent
interactions
(NCIs)
manifesting
form
C–H···Cl,
C–H···N,
l.p(Cl)···π
contacts.
Transition-metal-catalyzed
represents
an
atom-economic
clean
approach
preparation
aldehydes
efficiency.
Herein,
authors
Encyclopedia of Reagents for Organic Synthesis,
Год журнала:
2025,
Номер
unknown, С. 1 - 9
Опубликована: Янв. 3, 2025
Abstract
image
[
866081‐62‐1
]
C
18
H
28
N
2
P
(MW
334.38)
InChI
=
1S/C18H28N2P2/c1‐17(2,3)21(7)15‐16(22(8)18(4,5)6)20‐14‐12‐10‐9‐11‐13(14)19‐15/h9‐12H,1‐8H3/t21‐,22‐/m0/s1
InChIKey
DRZBLHZZDMCPGX‐VXKWHMMOSA‐N
(reagent
may
be
used
as
a
chiral
ligand
for
rhodium,
palladium,
copper,
and
silver
complexes
to
perform
enantioselective
reductions,
conjugate
additions,
allylic
alkylations)
Alternate
Name:
QuinoxP*.
Physical
Data:
mp
102–103°C;
[α]
D
−54.3°
(
c
1.00,
CHCl
3
);
1
NMR
(395.75
MHz,
CDCl
)
δ
1.00–1.03
(m,
),
1.42–1.44
6
7.70–7.74
8.08–8.12
13
(99.45
4.77
(t,
J
4.1
Hz),
27.59
7.4
31.90
129.50,
129.60,
141.63,
165.12
(dd,
5.7,
2.4
Hz);
31
(202.35
δ−17.7
(s);
IR
(KBr)
2950,
1470,
780
cm
−1
;
HRMS
(FAB)
calcd.
29
(M
+
H);
335.1809;
found:
335.1826.
Anal.
:
C,
64.66;
H,
8.44.
Found:
64.57;
8.29.
Solubility:
sol
toluene,
ether,
THF,
dichloromethane,
hexane.
Form
Supplied
in:
orange
solid;
commercially
available.
Preparative
Methods:
solution
of
n
‐BuLi
(1.25
mL
1.60
M
hexane
solution,
2.0
mmol)
was
added
dropwise
stirred
t
‐butylmethylphosphine–borane
(236
mg,
in
THF
(4
mL)
at
−78
°C
under
nitrogen.
After
15
min,
2,3‐dichloroquinoxaline
(133
0.67
one
portion
with
vigorous
stirring
the
mixture
warmed
rt
during
h.
additional
h,
tetramethylethylenediamine
(1
continued
The
reaction
quenched
HCl
extracted
combined
extracts
were
washed
brine,
dried
over
Na
SO
4
.
solvent
removed
vacuum
residue
purified
by
chromatography
on
silica
gel
(hexane/EtOAc
30/1)
give
desired
product
(179
8%)
an
solid,
which
further
recrystallization
from
hot
MeOH
(1.7
cubes.
Handling,
Storage,
Precautions
stable
air
moisture
more
than
8
months.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
recent
advances
in
the
hydrofunctionalisation
of
cyclopropenes
through
formation
carbon–heteroatom
bonds
for
synthesis
polysubstituted
cyclopropanes.
Abstract
Hydrophosphination
and
oxyphosphination
are
two
important
topical
reactions
in
order
to
prepare
organophosphorus
derivatives
from
unsaturated
such
as
alkenes
alkynes
a
more
sustainable
fashion.
Noticeably,
metal
catalysed
versions
have
shown
great
interest
efficiency.
By
contrast,
the
use
of
earth
abundant
transition
based
catalysts
for
transformations
is
less
reported,
even
if
there
growing
during
last
decade.
This
review
article
reports
highlights
recent
developments
using
manganese,
iron,
cobalt,
nickel
copper
hydro‐
oxyphosphination,
notably
exhibiting
selectivity,
functional
group
tolerance,
milder
conditions
catalyst
design.
Even
significant
progresses
were
made,
scopes
still
rather
limited
(mainly
focused
on
activated
olefins
styrenes)
chemo‐
stereo‐selectivity
issues
be
solved,
asymmetric
transformations.
Of
interest,
visible
light
including
blue
one
activator
emerged,
giving
promising
stimulating
results
at
ambient
conditions.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(7)
Опубликована: Дек. 22, 2023
Abstract
This
paper
presents
a
Mn(I)‐catalysed
methodology
for
the
enantioselective
hydrophosphination
of
terminal
alkenyl
aza‐heteroarenes.
The
catalyst
operates
through
H−P
bond
activation,
enabling
successful
diverse
range
alkenyl‐heteroarenes
with
high
enantioselectivity.
presented
protocol
addresses
inherently
low
reactivity
and
commonly
encountered
suboptimal
enantioselectivities
these
challenging
substrates.
As
an
important
application
we
show
that
this
method
facilitates
synthesis
non‐symmetric
tridentate
P,N,P‐containing
ligand
like
structure
in
just
two
synthetic
steps
using
single
catalytic
system.
