ACS Catalysis,
Год журнала:
2020,
Номер
10(22), С. 13202 - 13212
Опубликована: Окт. 30, 2020
The
Pd(0)-catalyzed
coupling
cyclization
of
1,2-allenyl
ketones
with
aryl
halides
to
construct
multisubstituted
furan
derivatives
has
been
developed.
Nevertheless,
the
detailed
mechanism
this
reaction,
proceeding
via
either
Pd(II)-carbenoid
or
π-allyl-Pd(II)
intermediate,
still
remains
debatable.
Herein,
computational
studies
were
performed
provide
mechanistic
insights
into
reactions,
and
substituent-dependent
pathways
revealed.
Computational
results
suggest
that
substituents,
R1–R3
attached
R4
moiety
halides,
could
play
significant
roles
in
variation
pathway.
It
would
be
favorable
form
intermediate
when
R1
is
an
aryl/alkyl
group
steric
hindrance
present
between
R2
R3.
For
substrate
halide,
bearing
electron-donating
(R4)
at
para
position
more
ready
undergo
migratory
insertion
than
electron-withdrawing
group.
factors
responsible
for
formation
both
intermediates
are
discussed.
Synthesis,
Год журнала:
2021,
Номер
53(24), С. 4567 - 4587
Опубликована: Авг. 3, 2021
Abstract
This
review
article
summarizes
progress
made
on
[1,2]-sigmatropic
rearrangements
using
carbenes
in
the
ylide
formation
step.
While
other
rearrangements,
such
as
[2,3]-sigmatropic,
Doyle–Kirmse,
or
Sommelet–Hauser
have
been
studied
detail
over
past
decades,
investigations
are
still
limited.
Based
application
of
diazoalkanes
carbene
precursors,
research
reactions
started
flourishing
1990s.
Short
Review
covers
milestones
from
advent
to
generate
ammonium,
oxonium
and
species,
should
serve
an
overview
further
promote
this
area.
1
Introduction
2
Ammonium
Ylides
3
Oxonium
4
Sulfonium
Selenium
5
Halonium
6
Conclusion
Outlook
Organic Letters,
Год журнала:
2019,
Номер
21(24), С. 9965 - 9969
Опубликована: Дек. 4, 2019
An
efficient
rhodium-catalyzed
unprecedented
oxa-[2,3]-sigmatropic
rearrangement
of
sulfur
ylide
derived
from
α-thioesters/ketones
and
diazo
carbonyl
compounds
has
been
accomplished
for
the
synthesis
various
sulfur-tethered
vinylogous
carbonates
in
good
to
excellent
yields.
Important
features
developed
reaction
include
wide
functional
group
tolerance,
chemo-
regioselectivity,
involving
motif.
The
present
also
equally
works
well
with
α-selenoesters
seleno-containing
carbonates.
ACS Catalysis,
Год журнала:
2020,
Номер
10(22), С. 13202 - 13212
Опубликована: Окт. 30, 2020
The
Pd(0)-catalyzed
coupling
cyclization
of
1,2-allenyl
ketones
with
aryl
halides
to
construct
multisubstituted
furan
derivatives
has
been
developed.
Nevertheless,
the
detailed
mechanism
this
reaction,
proceeding
via
either
Pd(II)-carbenoid
or
π-allyl-Pd(II)
intermediate,
still
remains
debatable.
Herein,
computational
studies
were
performed
provide
mechanistic
insights
into
reactions,
and
substituent-dependent
pathways
revealed.
Computational
results
suggest
that
substituents,
R1–R3
attached
R4
moiety
halides,
could
play
significant
roles
in
variation
pathway.
It
would
be
favorable
form
intermediate
when
R1
is
an
aryl/alkyl
group
steric
hindrance
present
between
R2
R3.
For
substrate
halide,
bearing
electron-donating
(R4)
at
para
position
more
ready
undergo
migratory
insertion
than
electron-withdrawing
group.
factors
responsible
for
formation
both
intermediates
are
discussed.
