Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(21)
Published: Feb. 27, 2024
Abstract
Chiral
trisubstituted
vicinal
diols
are
a
type
of
important
organic
compounds,
serving
as
both
common
structure
units
in
bioactive
natural
products
and
chiral
auxiliaries
asymmetric
synthesis.
Herein,
by
using
siloxypropadienes
the
precursors
allyl
copper(I)
species,
copper(I)‐catalyzed
diastereoselective
enantioselective
reductive
allylation
ketones
was
achieved,
providing
syn
‐diols
anti
good
to
excellent
enantioselectivity.
DFT
calculations
show
that
cis
‐γ‐siloxy‐allyl
copper
species
generated
favorably
with
either
1‐TBSO‐propadiene
or
1‐TIPSO‐propadiene.
Moreover,
steric
difference
TBS
group
TIPS
distinguishes
face
selectivity
acetophenone,
leading
‐selectivity
for
Easy
transformations
were
performed,
demonstrating
synthetic
utility
present
method.
one
diol
prepared
above
used
suitable
organocatalyst
catalytic
self‐coupling
aldimines
situ
B
2
(neo)
.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(15), P. 10325 - 10338
Published: July 17, 2023
[1,2]-Phospha-Brook
rearrangement
entails
the
generation
of
α-oxygenated
carbanions
via
umpolung
process.
Recently,
these
anionic
species
have
been
widely
utilized
for
several
C–C
bond
forming
strategies,
providing
various
useful
frameworks
that
are
difficult
to
access
through
conventional
approaches.
However,
application
this
powerful
methodology
in
development
chiral
strategies
is
still
at
nascent
stage
due
challenges
involved
controlling
chemoselectivity
and
enantioselectivity.
This
synopsis
provides
a
detailed
summary
diastereo-
and/or
enantioselective
chemical
transformations
using
[1,2]-phospha-Brook
rearrangement.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(21)
Published: Feb. 27, 2024
Chiral
trisubstituted
vicinal
diols
are
a
type
of
important
organic
compounds,
serving
as
both
common
structure
units
in
bioactive
natural
products
and
chiral
auxiliaries
asymmetric
synthesis.
Herein,
by
using
siloxypropadienes
the
precursors
allyl
copper(I)
species,
copper(I)-catalyzed
diastereoselective
enantioselective
reductive
allylation
ketones
was
achieved,
providing
syn-diols
anti-diols
good
to
excellent
enantioselectivity.
DFT
calculations
show
that
cis-γ-siloxy-allyl
copper
species
generated
favorably
with
either
1-TBSO-propadiene
or
1-TIPSO-propadiene.
Moreover,
steric
difference
TBS
group
TIPS
distinguishes
face
selectivity
acetophenone,
leading
syn-selectivity
for
anti-selectivity
Easy
transformations
were
performed,
demonstrating
synthetic
utility
present
method.
one
diol
prepared
above
used
suitable
organocatalyst
catalytic
self-coupling
aldimines
situ
B
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(34), P. 6262 - 6266
Published: Aug. 21, 2023
The
multicomponent
catalytic
asymmetric
Pudovik
addition/[1,2]-phospha-Brook
rearrangement/Michael
reaction
sequence
of
isatins,
phosphites,
and
4-oxobutenoates
was
realized.
A
series
oxindole
derivatives
containing
two
contiguous
stereocenters
obtained
in
high
yields
excellent
stereoselectivities
(up
to
>99%
yield,
>95:5
dr,
ee)
using
a
chiral
Lewis
acid
catalyst.
possible
model
is
presented
illustrate
the
stereocontrol.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(41), P. 8827 - 8831
Published: Oct. 10, 2024
Phosphorylated
tyrosine
is
a
fundamental
building
block
of
bioactive
peptides
and
proteins.
However,
the
chemoselective
phosphorylation
over
other
nucleophilic
amino
acid
residues
in
unprotected
remains
significant
challenge.
Here
we
report
an
umpolung
strategy
that
converts
C-terminal
into
electrophilic
spirolactone
cyclohexadienone
motif
through
hypervalent
iodine
oxidation,
followed
by
1,2-phospha-Brook
rearrangement
using
phosphite
diesters
as
phosphoryl
donors.
This
reaction
proceeds
chemoselectively
at
phenol
applicable
to
wide
range
peptide
substrates
containing
various
residues,
including
serine
threonine.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(42), P. 7595 - 7600
Published: Oct. 13, 2023
O-Phosphination
of
α-dicarbonyls
via
sequential
in
situ
formation
a
Kukhtin-Ramirez
adduct
and
P(NMe2)3-catalyzed
process
has
been
exploited
for
the
synthesis
α-phosphoryloxy
carbonyls.
A
range
P(O)-H
derivatives,
including
diarylphosphine
oxides,
arylphosphinates,
phosphinates,
are
competent
candidates
to
be
introduced
into
this
transformation,
various
carbonyls
obtained.
This
approach
possesses
advantages
mild
conditions,
simple
operations,
atom
economy,
high
efficiency,
gram-scale
synthesis,
which
make
it
promising
toolbox.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(19), P. 14177 - 14182
Published: Sept. 18, 2024
An
approach
involving
the
use
of
a
bifunctional
aminocatalyst
containing
Brønsted
base
and
iminium
activation
sites
for
asymmetric
multicomponent
reactions
[1,2]-phospha-Brook
rearrangement
has
yet
to
be
realized.
Herein,
we
present
an
aminocatalytic
enantioselective
conjugate
addition
α-phosphonyloxy
enolates
formed
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 1, 2025
A
highly
efficient
and
stereoselective
[1,2]-phospha-Brook
rearrangement
of
fluoromethyl
ketones
has
been
achieved
by
utilizing
a
new
type
P-chiral
H-phosphonate
derived
from
CAMDOL,
designated
as
CAMDOL-PHO.
library
38
secondary
alcohols
featuring
an
α-trifluoromethyl
or
trifluoroaryl
motif
were
afforded
in
up
to
97%
yield
with
99:1
dr.
Compared
other
known
chiral
auxiliaries,
bicyclic
CAMDOL
exhibits
superior
induction
ability
due
its
unique
center-chiral
scaffold.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(8), P. 1857 - 1862
Published: Feb. 21, 2024
Abstract
An
intermolecular
addition
reaction
involving
an
unconventional
combination
of
a
diarylmethyl
anion
and
electrophile,
which
is
mediated
by
the
[1,2]‐phospha‐Brook
rearrangement
under
Brønsted
base
catalysis,
was
developed.
Diarylmethyl
anions
having
benzofuran
moiety
were
generated
through
with
aid
catalytic
amount
phosphazene
P2‐
t
Bu.
The
resulting
carbanion
intermediates
trapped
various
electrophiles,
such
as
α,β‐unsaturated
ketones,
aryl
aldehydes,
α‐ketoesters,
N
‐Boc
imines,
providing
corresponding
diarylalkane
derivatives
in
good
yields.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(6), P. 1367 - 1367
Published: March 18, 2025
It
was
shown
for
the
first
time
that
diaryl(hetaryl)ketones
are
capable
of
directly
phosphorylating
with
red
phosphorus
in
superbase
suspension
KOH/DMSO(H2O)
at
85
°C
1.5
h
to
afford
potassium
bis(diaryl(hetaryl)methyl)phosphates
were
earlier
inaccessible
a
yield
up
45%.
The
ESR
data
demonstrate
unlike
previously
published
phosphorylation
elemental
phosphorus,
this
new
reaction
proceeds
via
single
electron
transfer
from
polyphospide
anions
diaryl(hetaryl)ketones.
This
is
example
C-O-P
bond
generation
during
strongly
basic
media,
which
usually
provides
C-P
formation.
International Journal of Molecular Sciences,
Journal Year:
2025,
Volume and Issue:
26(7), P. 3065 - 3065
Published: March 27, 2025
The
[1,2]-phospha-Brook
rearrangement
serves
as
a
powerful
synthetic
strategy
that
enables
efficient
carbonyl
umpolung
through
phosphoryl
group
migration,
providing
direct
access
to
α-hydroxyphosphoryl
compounds-a
privileged
class
of
synthons
with
broad
applications
in
organophosphorus
chemistry,
medicinal
and
materials
science.
This
review
provides
comprehensive
overview
recent
progress
methodologies,
possible
mechanisms,
asymmetric
transformations,
highlighting
key
breakthroughs
future
directions
this
rapidly
evolving
field.
