The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
87(1), С. 373 - 385
Опубликована: Дек. 13, 2021
Using
DFT
and
ab
initio
calculations,
we
demonstrate
that
noncyclic
formamidines
can
undergo
thermal
rearrangement
into
their
isomeric
aminocarbenes
under
rather
mild
conditions.
We
synthesized
the
silylformamidine,
for
which
lowest
activation
energy
in
this
process
was
predicted.
Experimental
studies
proved
it
to
serve
as
a
very
reactive
nucleophilic
carbene.
The
reactions
with
acetylenes,
benzenes,
trifluoromethane
proceeded
via
insertion
sp,
sp2,
sp3
CH
bonds.
carbene
also
reacted
functional
groups,
such
CHO,
COR,
CN
at
double
or
triple
bonds,
displaying
high
mobility
of
trimethylsilyl
group.
obtained
silylformamidine
be
considered
latent
It
prepared
bulk
quantities,
stored,
used
when
need
arises.
Calculation
results
predict
similar
behavior
some
other
silylated
related
compounds.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2752 - 2906
Опубликована: Авг. 10, 2021
Photoinduced
chemical
transformations
have
received
in
recent
years
a
tremendous
amount
of
attention,
providing
plethora
opportunities
to
synthetic
organic
chemists.
However,
performing
photochemical
transformation
can
be
quite
challenge
because
various
issues
related
the
delivery
photons.
These
challenges
barred
widespread
adoption
steps
industry.
past
decade,
several
technological
innovations
led
more
reproducible,
selective,
and
scalable
photoinduced
reactions.
Herein,
we
provide
comprehensive
overview
these
exciting
advances,
including
flow
chemistry,
high-throughput
experimentation,
reactor
design
scale-up,
combination
photo-
electro-chemistry.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(10)
Опубликована: Янв. 7, 2022
Although
the
synthesis
of
common
cyclopropenes
has
been
well
studied,
access
to
cyclopropenols
is
rather
limited.
Herein,
we
report
first
α-trifluoromethylated
via
2+1
cycloaddition
reactions
between
alkynes
and
trifluoroacylsilanes,
enabled
by
visible-light-induced
organocatalysis.
The
novel
ambiphilic
donor-acceptor
carbenes
derived
from
trifluoroacetylsilanes
reacted
efficiently
with
both
activated
non-activated
alkynes.
reaction
features
simple
operation,
mild
conditions,
broad
substrate
scope
good
functional
group
tolerance.
synthetic
potential
highlighted
gram-scale
cyclopropanols
through
combination
cyclization
high
diastereoselective
hydrogenation
in
one
pot.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(13)
Опубликована: Янв. 3, 2023
Abstract
Oxycarbenes
have
emerged
as
useful
intermediates
in
synthetic
chemistry.
Compared
to
the
widely
studied
oxycarbene
metal
complexes
bearing
Group
6
metals,
and
catalytic
applications
of
oxycarbenes
beyond
Fischer
carbene
are
less
explored
because
difficulty
controlling
their
reactivity
need
use
a
stoichiometric
amount
presynthesized
complex
starting
material.
This
Minireview
summarizes
early
late‐transition‐metal
highlights
recent
advances
free
reactions
transition‐metal‐catalyzed
involving
oxycarbenes.
We
hope
this
will
inspire
further
developments
emerging
area.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(6), С. 4026 - 4035
Опубликована: Фев. 1, 2024
Herein,
we
report
a
divergent
synthesis
of
fluoroalkyl
ketones
through
visible-light-induced
reactions
between
readily
available
organoboronic
esters
and
acylsilanes.
Selective
control
the
reactivity
in
situ
generated
organoboronate
complexes
is
key
to
achieving
transformations.
Under
basic
conditions,
undergo
deboronative
fluoride
elimination,
resulting
formation
enol
silyl
ethers
as
intermediates
that
react
with
various
electrophiles
generate
defluorinated
products.
Moreover,
combination
peroxide,
1,2-shift
group
favored
over
elimination
ketal
intermediates,
leading
This
transition-metal-free
reaction
operationally
simple,
aryl,
alkenyl,
alkyl
boronic
are
all
suitable
substrates.
The
synthetic
potential
has
been
demonstrated
by
gram-scale
facile
bioactive
molecules
including
zifrosilone
its
analogs.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
aims
to
provide
an
overview
of
radical
Brook
rearrangement,
which
is
organized
by
grouping
three
type
reactive
species
generated
via
the
unique
rearrangement
process.
Chemical Science,
Год журнала:
2022,
Номер
13(11), С. 3273 - 3280
Опубликована: Янв. 1, 2022
Visible
light
induced
singlet
nucleophilic
carbenes
undergo
rapid
[2
+
1]-cycloaddition
with
tethered
olefins
to
afford
unique
bicyclo[3.1.0]hexane
and
bicyclo[4.1.0]heptane
scaffolds.
This
cyclopropanation
process
requires
only
visible
irradiation
proceed,
circumventing
the
use
of
exogenous
(photo)catalysts,
sensitisers
or
additives
showcases
a
vastly
underexplored
mode
reactivity
for
in
chemical
synthesis.
The
discovery
additional
transformations
including
cyclopropanation/retro-Michael/Michael
cascade
chromanones
photochemical
C-H
insertion
reaction
are
also
described.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(3), С. 819 - 836
Опубликована: Янв. 1, 2023
This
review
provides
recent
advances
and
insights
into
photoirradiation
reactions
of
acylsilanes,
notably
via
key
nucleophilic
siloxycarbene
intermediates.
Nucleophilic
addition,
insertion
reaction,
cyclization
are
discussed
in
terms
reaction
mechanism
scope.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 4926 - 4975
Опубликована: Янв. 1, 2024
In
search
for
the
perfect
wave(length).
This
review
is
dedicated
to
recent
efforts
in
development
of
visible
light
driven
photochemical
strategies
occurring
coloured
organic
compounds.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(23)
Опубликована: Апрель 6, 2023
Investigations
into
C-H
amidation
reactions
catalysed
by
cationic
half-sandwich
d6
metal
complexes
revealed
that
the
indenyl-derived
catalyst
[Ind*RhCl2
]2
significantly
accelerated
directed
ortho
of
benzoyl
silanes
using
1,4,2-dioxazol-5-ones.
Ring
slippage
involving
a
haptotropic
η5
to
η3
rearrangement
indenyl
complex
proposedly
enables
ligand
substitution
at
centre
proceed
via
associative,
rather
than
dissociative
pathways,
leading
significant
rate
and
yield
enhancements.
Intriguingly,
this
phenomenon
appears
specific
for
weakly
coordinating
carbonyl-based
directing
groups
with
no
acceleration
observed
corresponding
strongly
nitrogen-based
groups.
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 2039 - 2044
Опубликована: Март 4, 2024
We
report
the
synthesis
of
acyl
hydrazides
from
acylsilanes
in
presence
visible
light
without
aid
additives
or
transition
metals.
Acylsilanes
underwent
[1,2]-Brook
rearrangement
to
generate
nucleophilic
siloxycarbenes
which
on
further
addition
N═N
azodicarboxylates
produced
hydrazides.
Control
experiments
indicate
that
reaction
proceeds
through
singlet
carbene
intermediate.
Transformation
hydrazide
functionality
other
functional
groups
was
demonstrated,
including
drug
candidate
Moclobemide.
