Angewandte Chemie,
Год журнала:
2024,
Номер
136(21)
Опубликована: Фев. 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)
.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 16, 2025
Brønsted
base-mediated
[1,2]-phospha-Brook
rearrangements
have
garnered
considerable
attention
for
developing
new
methodologies
and
efficiently
constructing
complex
molecular
structures.
However,
the
strict
reliance
on
pentavalent
phosphonates
imposes
strong
limitations
reaction
types,
mechanistic
constraint
also
excludes
involvement
of
trivalent
phosphine
in
same
pathway.
In
this
study,
we
employ
Lewis
acid
rather
than
base
to
shift
charge
transfer
from
previous
O-P-C
direction
a
P-C-O
process.
This
orthogonal
approach
can
undergo
unprecedented
C-O
bond
cleavage
instead
traditional
C-P
splitting
enables
deoxygenative
phosphorylation
carbonyl
compounds
under
metal-free
conditions
rapid
access
various
tertiary
oxides.
The
demonstrates
excellent
substrate
scope,
remarkable
functional
group
compatibility,
operational
simplicity,
offering
significantly
enhanced
atom-economy
compared
strategies.
Additionally,
detailed
studies
reveal
an
unusual
oxygen
atom
crossover
clearly
elucidate
mechanism
acid-mediated
phospha-Brook
rearrangement.
These
insights
further
deepen
understanding
phosphorus
chemistry
pave
way
design
related
reactions.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(34), С. 19060 - 19066
Опубликована: Авг. 21, 2023
Tri(t-butyl)phosphine
and
terminal
alkynes
undergo
1,2-phosphorus-migrative
[3
+
2]
cycloaddition
in
the
presence
of
a
proton
source
under
photocatalytic
conditions.
The
reaction
exhibits
broad
functional
group
tolerance
affords
substituted
cyclic
phosphonium
salts,
which
are
amenable
to
further
derivatization
by
Wittig
olefination.
Theoretical
studies
suggest
that
phosphorus
1,2-migration
β-phosphonioalkyl
radical
proceeds
through
phosphine
cation-alkene
complex
as
pseudointermediate,
two
fragments
intermediate
bound
each
other
multiple
noncovalent
interactions.
Bulletin of the Chemical Society of Japan,
Год журнала:
2024,
Номер
97(7)
Опубликована: Июль 1, 2024
Abstract
In
this
study,
we
developed
a
method
to
synthesize
deoxygenative
functionalized
products
by
reacting
aromatic
dicarbonyls
with
DBU,
TMSOTf,
diphenylphosphine
oxide,
and
range
of
nucleophiles.
Moreover,
demonstrated
that
sequential
application
phospha-Brook
rearrangement
benzylic
substitution
conditions
aldehydes
affords
the
effectively.
With
highly
nucleophilic
reagents,
it
was
possible
proceed
functionalization
without
TMSOTf.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(22), С. 4723 - 4728
Опубликована: Авг. 13, 2024
Abstract
We
have
developed
a
method
for
the
synthesis
of
thieno[3,2‐
b
]furans
on
basis
strategy
consisting
formal
[3+2]
cycloaddition
utilizing
[1,2]‐phospha‐Brook
rearrangement
and
subsequent
Brønsted
base‐mediated
cyclization.
The
streamlines
access
to
wide
range
well‐organized
2,3,5,6‐tetrasubstituted
that
are
otherwise
difficult
synthesize
is
also
applicable
syntheses
seleno[3,2‐
]furans.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(25)
Опубликована: Май 22, 2023
Abstract
A
methodology
for
the
formal
addition
of
β‐acylalkenyl
anions
was
developed
by
utilizing
[1,2]‐phospha‐Brook
rearrangement
under
Brønsted
base
catalysis.
The
two‐step
reaction
involves
catalytic
α‐oxygenated
propargyl
generated
via
to
electron‐deficient
ketones
and
subsequent
alcoholysis
afford
tertiary
alcohols
having
an
enone
moiety.
This
is
a
rare
example
carbon‐carbon
bond
forming
anion
equivalents,
providing
synthetic
building
blocks
that
are
otherwise
difficult
access.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(21)
Опубликована: Фев. 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)
.
