Royal Society of Chemistry eBooks,
Journal Year:
2024,
Volume and Issue:
unknown, P. 193 - 253
Published: Dec. 6, 2024
Main
group
elements
have
recently
emerged
as
benign
and
cost-effective
alternatives
to
transition
metals
in
organometallic
chemistry.
By
finely
tuning
their
electronic
structure,
these
can
engage
substrate
coordination,
activate
small
molecules,
even
catalyse
redox
reactions,
mirroring
the
behaviour
of
metals.
This
book
chapter
aims
summarize
a
relatively
underexplored
area
within
main
metal
chemistry:
ability
undergo
photoinduced
processes
such
reactivity,
rearrangements,
radical
formation.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(8), P. 887 - 902
Published: Nov. 29, 2023
Comprehensive
Summary
Organofluorine
compounds
are
central
in
synthetic
chemistry,
medicinal
chemistry
and
material
chemistry.
In
this
review,
we
summarize
the
investigations
on
synthesis
of
organofluorine
with
acylsilanes.
For
non‐fluorinated
acylsilanes,
situ
generation
difluoroenoxysilanes
from
reactions
acylsilanes
trifluoromethylation
reagents
is
major
pathway,
leading
to
facile
preparation
various
α,α‐difluoroketones.
fluoroalkylacylsilanes,
apart
through
anion
Brook
rearrangement,
radical
rearrangement
photoexcited
selective
control
reactivities
biradicals
pave
way
for
a
variety
compounds.
general,
most
these
gave
racemic
products,
asymmetric
still
rare,
which
would
be
future
direction
field.
Key
Scientists
1957,
first
acylsilane
compound,
triphenylsilyl
phenyl
ketone
was
reported
by
group.
1991,
Portella
coworkers
reaction
perfluoroorganometallic
without
resulting
formation
alcohols
as
products.
1992,
Xu
carried
out
investigation
fluoroalkylacylsilanes
rearrangement.
1994,
group
Ruppert‐Prakash
reagent.
2009,
Otaka
NHC‐mediated
intramolecular
redox
prepare
(
Z
)‐fluoroalkene
dipeptide
isosteres
(FADIs)
γ,γ‐difluoro‐α,β‐
enoylsilane.
Until
2022,
application
fluoroalkylsiloxycarbenes
achieved
Shen
group,
enabling
fluoroalkylated
cyclopropenols.
successfully
trapping
biradical
intermediates
generated
fluorine‐containing
fused
gem
‐difluorooxetanes.
same
year,
asymetric
enantiomerically
enriched
fluoroalkyl
difluoroenoxysilanes.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 5796 - 5805
Published: March 25, 2025
The
transition
metal-catalyzed
asymmetric
[n
+
2]
cycloaddition
reaction
with
oxy-substituted
ketene
intermediates
remains
a
synthetic
challenge
due
to
the
limited
availability
of
suitable
precursors.
Herein,
we
report
visible-light-driven,
palladium-catalyzed
[4
vinyl
benzoxazinanones
siloxyketene
intermediates,
generating
structurally
diverse
chiral
quinolinone
derivatives
satisfactory
diastereo-
and
enantioselectivities.
transient
generation
siloxyketenes
from
α-ketoacylsilylanes
through
visible-light-induced
Brook
rearrangement
is
important
for
success
present
cycloaddition.
13C-labeling
experiments
reveal
pathway
involving
[1,3]-silyl
migration
process.
side
arm
effects
BOX
ligand
silyl
steric
hindrance
α-ketoacylsilanes
play
crucial
roles
in
stereoselectivity
control,
theoretical
calculations
provide
insights
into
stereochemical
outcome
reaction.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(19), P. 14205 - 14209
Published: Sept. 22, 2023
Acylsilanes
are
able
to
react
as
nucleophilic
carbene
precursors,
electrophiles,
and
directing
groups
in
C–H
functionalization.
To
date,
some
of
the
products
reportedly
formed
during
transition-metal-catalyzed
photochemical
reactions
involving
acylsilanes
have
been
incorrectly
assigned.
provide
clarity,
we
herein
address
these
structural
misassignments
detail
revised
structures.
New
insights
into
reactivity
were
also
afforded
via
discovery
that
light-induced
siloxy
carbenes
participate
intramolecular
1,2-carbonyl
addition
proximal
esters.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(8), P. 2339 - 2343
Published: Jan. 1, 2024
A
formal
carbon
insertion
of
acylsilanes
into
B–B
and
B–Si
bonds
has
been
developed.
The
in
situ
formed
siloxycarbene
under
blue
LED
irradiation
worked
as
the
intermediate
for
reaction.
When
2-furyl
2-thiophenyl
were
used,
B(pin)
ring
was
enlarged
to
a
six-membered
ring.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5827 - 5832
Published: July 2, 2024
We
disclosed
herein
an
enantioselective
formal
siloxycarbene
insertion
reaction
enabled
by
chiral
phosphoric
acid
and
blue
LED
irradiation.
This
is
the
first
time
asymmetric
into
sp
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 18216 - 18222
Published: Nov. 25, 2024
A
catalytic
protocol
has
been
developed
to
access
Fischer
carbene
nickel
complexes
using
acylsilanes
as
stable
and
readily
available
precursors.
The
as-generated
exhibit
versatile
reactivity,
including
cyclopropanation
with
alkenes,
α-C–H
insertion
reactions,
two-component
C–H
addition
norbornene,
which
demonstrates
the
broad
utility
of
nickel(0)/acylsilane
system
for
applications
complexes.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(22), P. 2712 - 2716
Published: July 9, 2024
Comprehensive
Summary
A
novel
method
for
synthesizing
α‐oxygen
organoboron
compounds
has
been
developed
through
acylsilane‐based
carbene
insertion
reactions
into
C—B
bonds.
As
coupling
partners,
readily
available
(alkenyl,
allyl,
and
allenyl
B(pin))
were
employed.
Based
on
the
substrates,
pure
bonds
or
followed
by
a
siloxy
group
rearrangement
process
(from
carbon
to
boron)
would
occur,
delivering
with
great
diversities.
Control
experiments
demonstrated
that
electronic
effect
of
substituents
mainly
controlled
process.
Besides,
no
matter
which
isomer
substrate
(
Z
E
)
was
used,
reaction
β‐aryl‐substituted
alkenyl
B(pin)
affords
both
isomers
products
E,
separable
column
chromatography).
Trapping
indicated
triplet
energy
transfer
involved.
Physical Chemistry Chemical Physics,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
Regulatory
mechanisms
for
the
photogeneration
of
singlet/triplet
siloxy
carbenes
and
their
involvement
in
[2+1]
photocyclizations
have
been
thoroughly
studied
at
CASPT2//CASSCF/PCM
level
theory.
