Fluoroalkylacylsilanes as Novel Ambiphilic Donor–Acceptor Carbene Precursors
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
ConspectusCarbenes,
as
highly
reactive
intermediates,
have
emerged
pivotal
tools
in
organic
synthesis,
catalysis,
and
materials
science
due
to
their
versatile
reactivity
broad
applicability.
Among
the
diverse
classes
of
carbenes,
donor-acceptor
carbenes
(DACs)
attracted
significant
attention
owing
unique
electronic
properties
exceptional
reaction
selectivity.
The
distinctive
DACs
arises
from
synergistic
interplay
between
electron-withdrawing
electron-donating
groups
attached
carbene
center,
enabling
a
wide
array
transformations.
These
attributes
established
indispensable
building
blocks
for
constructing
complex
molecular
architectures
achieving
precise
control
over
chemical
transformation.This
Account
highlights
our
recent
advancements
development
fluoroalkylacylsilanes
novel
precursors
DACs.
Under
photocatalytic
conditions,
these
generate
fluoroalkyl
siloxycarbenes
via
radical
Brook
rearrangement.
group,
known
its
strong
properties,
imparts
electrophilic
characteristics,
while
siloxyl
group
stabilizes
center.
Together,
functionalities
render
ideal
candidates
generation
DACs,
providing
platform
range
transformations,
including
cycloadditions,
bond
insertions,
construction
new
structures.First,
we
developed
visible-light-induced,
organocatalyzed
[2
+
1]
cyclization
alkynes
trifluoroacetylsilanes,
leading
synthesis
cyclopropenols.
Mechanistic
studies
provided
compelling
evidence
involvement
triplet
intermediates
this
reaction,
demonstrating
utility
functionalized
cyclic
compounds.
Second,
explored
cyclopropanation
reactions
elucidated
diastereoselective
transfer
trifluoroacetylsilane-derived
alkenes.
Density
functional
theory
(DFT)
calculations
revealed
key
insights
into
origins
observed
diastereoselectivity,
offering
molecular-level
understanding
stereochemical
outcomes.
Additionally,
extended
scope
include
organoboronic
esters,
divergent
ketones.
By
modulating
situ-generated
organoboronate
complexes─formed
through
with
esters─we
achieved
selective
both
fluorine-maintaining
defluorinated
This
transition-metal-free
approach
is
operationally
simple
compatible
substrates,
aryl,
alkenyl,
alkyl
boronic
esters.
Beyond
C-B
functionalization,
applied
C(sp2)-H
functionalization
1,3-azoles.
investigations
suggest
that
success
stems
dual
role
trifluoroacetylsilanes
under
conditions:
they
not
only
participate
but
also
produce
biradicals
facilitate
ring-opening
aromatization
fused
cyclopropanes.We
anticipate
work
on
ambiphilic
will
lay
groundwork
further
use
acylsilanes
chemistry.
developments
are
expected
inspire
strategies
design
expand
silanes
synthetic
opening
avenues
intricate
architectures.
Язык: Английский
Visible-Light-Induced [2 + 2] Cyclization of Alkynes with Bromodifluoroacetylsilanes: Facile Access to gem-Difluorocyclobutenones
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(19), С. 15955 - 15962
Опубликована: Апрель 29, 2025
Herein,
we
report
a
simple
and
efficient
method
for
the
synthesis
of
gem-difluorocyclobutenones
from
alkynes
bromodifluoroacetylsilanes,
proceeding
via
formal
cyclization
with
in
situ
generated
difluoroketene
under
visible-light-induced
conditions.
The
reaction
conditions
are
mild
exhibit
broad
substrate
scope,
including
both
aromatic
aliphatic
alkynes.
Additionally,
demonstrates
good
functional
group
tolerance,
facile
scalability,
potential
diverse
downstream
transformations.
Mechanistic
studies
suggest
that
bromodifluoroacetylsilanes
act
as
photochemical
precursors
to
difluoroketene.
Язык: Английский
Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 6881 - 6894
Опубликована: Апрель 14, 2025
Язык: Английский
Recent Advances in Metal-Catalyzed Transformations of Acylsilanes via the Activation of C–Si Bonds
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 8706 - 8723
Опубликована: Май 8, 2025
Язык: Английский
Catalytic 1,2-Radical Acyloxy Migration: A Strategy to Access Novel Chemical Space and Reaction Profiles
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 22, 2025
ConspectusRadical
migration
represents
a
powerful
strategy
for
reaction
discovery
and
development
in
organic
synthesis,
offering
access
to
unprecedented
functional
molecules
chemical
space.
In
this
Account,
we
describe
our
contributions
the
field,
particularly
focusing
on
1,2-radical
acyloxy
(RAM),
process
involving
transposition
of
radical
an
group.
We
highlight
its
application
carbohydrate
modification
allyl
carboxylate
trifunctionalization,
demonstrating
how
reactivity
enables
streamlined
synthesis
novel
glycomimetics
facilitates
selective
1,2,3-trifunctionalization
carboxylates.
These
advances
establish
1,2-RAM
as
versatile
platform
catalytic
transformations,
unlocking
new
opportunities
molecule
design.Our
approach
leverages
excited-state
palladium
ground-state
nickel
catalysis
modify
carbohydrates,
specifically
at
C2
position.
This
C2-deoxy-hydrogenation,
deuteration,
iodination,
alkenylation,
allylation,
ketonylation,
arylation
reactions,
providing
direct
glycomimetics.
transformations
streamline
structurally
diverse
glycomimetics,
facilitating
carbohydrate-based
molecules.
Furthermore,
mild
conditions
high
group
tolerance
these
systems
make
them
attractive
late-stage
functionalization,
broadening
their
applicability
complex
synthesis.Beyond
have
extended
achieve
By
employing
phosphine
catalysis,
demonstrate
1,3-carbobromination
accompanied
by
shift.
proof-of-concept
study
lays
foundation
developing
broader
range
effectively
transforming
carboxylates
into
substituted
isopropyl
donors.
advancement
expands
synthetic
utility
carboxylates,
enabling
rapid
construction
molecular
scaffolds.In
summary,
opens
avenue
development,
granting
The
conditions,
broad
compatibility,
unique
it
valuable
tool
synthesis.
anticipate
that
merging
with
other
platforms
will
further
advance
bond
disconnection
strategies,
provide
molecules,
expand
frontiers
Язык: Английский