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.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(22), С. 2712 - 2716
Опубликована: Июль 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.
Chemical Communications,
Год журнала:
2022,
Номер
58(90), С. 12604 - 12607
Опубликована: Янв. 1, 2022
Acyl
silanes
can
be
engaged
as
weakly
coordinating
directing
groups
in
cobalt
catalysed
C–H
functionalisation
reactions
to
prepare
benzoyl
that
are
highly
amenable
subsequent
synthetic
manipulations
yet
inaccessible
via
existing
methods.
Chemical Communications,
Год журнала:
2021,
Номер
57(64), С. 7938 - 7941
Опубликована: Янв. 1, 2021
Studies
into
the
Cp*Rh(iii)-catalysed
hydroarylation
of
alkenes
with
aryl
acyl
silanes
led
to
discovery
a
new
synthetic
strategy
access
unique
silicon
derived
indene
frameworks.
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.
