Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(2), P. 637 - 641
Published: Jan. 3, 2022
A
Ni-mediated
decarboxylative
silylation
of
alkynyl
cyclic
carbonates
used
as
versatile
propargylic
surrogates
is
reported
affording
a
wide
range
highly
substituted
2,3-
and
3,4-allenol
products
in
good
yields.
The
formal
cross-coupling
between
tentative
intermediate
Ni(allenyl)
the
silyl
reagent
was
further
extended
to
enantiospecific
conversions
providing
access
chiral
allene
synthons.
This
protocol
marks
first
Ni-catalyzed
proceeding
through
an
SN2'
manifold.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
N-Sulfonyl
hydrazones
have
been
extensively
used
as
operationally
safe
carbene
precursors
in
modern
organic
synthesis
due
to
their
ready
availability,
facile
functionalization,
and
environmental
benignity.
Over
the
past
two
decades,
there
has
tremendous
progress
chemistry
of
N-sulfonyl
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Many
transfer
reactions
are
unique
cannot
be
achieved
by
any
alternative
methods.
The
discovery
novel
development
highly
enantioselective
new
skeletal
editing
represent
notable
recent
achievements
hydrazones.
This
review
describes
overall
made
hydrazones,
organized
based
on
reaction
types,
spotlighting
current
state-of-the-art
remaining
challenges
addressed
future.
Special
emphasis
is
devoted
identifying,
describing,
comparing
scope
limitations
methodologies,
key
mechanistic
scenarios,
potential
applications
complex
molecules.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(33), P. 12968 - 12973
Published: Aug. 12, 2021
We
report
herein
a
highly
efficient
palladium-catalyzed
carbene
insertion
into
strained
Si–C
bonds
with
excellent
enantioselectivity,
which
provides
rapid
and
distinct
method
to
access
silacyclopentanes
three-
or
four-substituted
stereocenter
asymmetrically.
Mechanistic
studies
using
hybrid
density
functional
theory
suggest
catalytic
cycle
involving
oxidative
addition,
migratory
insertion,
reductive
elimination.
In
roles
of
the
chiral
ligands
in
controlling
reaction
enantioselectivity
are
also
elucidated.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(30), P. 11799 - 11810
Published: July 23, 2021
Although
dirhodium-catalyzed
multicomponent
reactions
of
diazo
compounds,
nucleophiles
and
electrophiles
have
achieved
great
advance
in
organic
synthesis,
the
introduction
allylic
moiety
as
third
component
via
metal
intermediate
remains
a
formidable
challenge
this
area.
Herein,
an
attractive
three-component
reaction
readily
accessible
amines,
compounds
enabled
by
novel
dirhodium(II)/Xantphos
catalysis
is
disclosed,
affording
various
architecturally
complex
functionally
diverse
α-quaternary
α-amino
acid
derivatives
good
yields
with
high
atom
step
economy.
Mechanistic
studies
indicate
that
transformation
through
relay
dirhodium(II)-catalyzed
carbene
insertion
alkylation
process,
which
catalytic
properties
dirhodium
are
effectively
modified
coordination
Xantphos,
leading
to
activity
process.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(10), P. 2840 - 2855
Published: Jan. 1, 2022
This
review
summarizes
the
growing
landscape
in
reactions
of
silacyclobutanes
(SCBs)
by
highlighting
fascinating
progress,
deconstructing
mechanistic
underpinnings,
and
drawing
insight
from
related
ring-opening
expanding
SCBs.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(24)
Published: March 25, 2022
Catalytic
asymmetric
synthesis
of
chiral
endocyclic
allenes
remains
a
challenge
in
allene
chemistry
owing
to
unfavored
tension
and
complex
chirality.
Here,
we
present
new
relay
strategy
merging
Pd-catalyzed
[3+2]
annulation
with
enyne-Cope
rearrangement,
providing
facile
route
9-membered
high
efficiency
enantioselectivity.
Moreover,
theoretical
calculations
experimental
studies
were
performed
illustrate
the
critical,
but
unusual
Cope
rearrangement
that
allows
for
complete
central-to-axial
chirality
transfer.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(12)
Published: Jan. 29, 2024
Abstract
Azetidines,
being
four‐membered
N
‐heterocycles,
possess
significant
potential
in
contemporary
medicinal
chemistry
owing
to
their
favorable
pharmacokinetic
properties.
Regrettably,
the
incorporation
of
functionalized
azetidines
into
pharmaceutical
lead
structures
has
been
impeded
by
absence
efficient
synthetic
methods
for
synthesis.
In
this
study,
a
Rh‐catalyzed
one‐carbon
ring
expansion
aziridines
with
vinyl‐
‐triftosylhydrazones
is
presented,
which
facilitates
synthesis
high
value‐added
2‐alkenyl
azetidine
products.
This
research
represents
first
example
enabled
vinyl
carbenes.
Additionally,
one‐pot
two‐step
protocol,
initiated
from
cinnamaldehyde,
was
successfully
achieved,
offering
step‐economical
and
facile
approach
these
compounds.
The
pivotal
aspect
successful
transformation
lies
situ
formation
an
alkenyl
aziridinium
ylide
intermediate.
Experimental
investigations,
coupled
computational
studies,
suggest
that
diradical
pathway
involved
reaction
mechanism.
