Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 28642 - 28647
Опубликована: Окт. 9, 2024
Carbenes
and
carbenoids
are
commonly
employed
for
the
synthesis
of
cyclopropane-containing
compounds.
Here
we
report
metal-free,
intramolecular
cyclopropanation
tethered
alkenes
by
free
carbenes
derived
from
alkynes
to
construct
structurally
unique
multicyclic
cyclopropanes
with
perfect
atom
economy.
The
nature
tether
influences
both
rate
carbene
formation
subsequent
competing
reaction
events.
Some
substrates
lead
metastable
cyclopropane
intermediates
that
further
fragment
furnish
interesting
isomeric
products
mechanistically
novel
processes.
A
removable
siloxane
can
be
utilized
achieve
formal
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(9), С. 2346 - 2358
Опубликована: Янв. 1, 2023
In
this
Review,
the
underrecognized
utilities
of
cyclopropylcarbinyl
cation
chemistry
are
summarized
in
cyclopropane
synthesis
and
skeletal
rearrangements,
their
applications
natural
product
total
highlighted.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 9, 2024
Cyclopropanes
are
among
the
most
important
structural
units
in
natural
products,
pharmaceuticals,
and
agrochemicals.
Herein,
we
report
a
manganese-catalyzed
cyclopropanation
of
allylic
alcohols
with
sulfones
as
carbene
alternative
precursors
via
borrowing
hydrogen
strategy
under
mild
conditions.
Various
arylmethyl
trifluoromethyl
work
efficiently
this
transformation
thereby
deliver
corresponding
cyclopropylmethanol
products
58%
to
99%
yields.
Importantly,
major
benefit
is
that
versatile
free
alcohol
moiety
retained
resultant
which
can
undergo
wide
range
downstream
transformations
provide
access
series
functional
molecules.
Mechanistic
studies
support
sequential
reaction
mechanism
involves
catalytic
dehydrogenation,
Michael
addition,
cyclization,
hydrogenation.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
recent
advances
in
the
hydrofunctionalisation
of
cyclopropenes
through
formation
carbon–heteroatom
bonds
for
synthesis
polysubstituted
cyclopropanes.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
A
nickel-catalyzed,
branched-selective
hydroalkylation
of
alkenes
using
diazo
compounds
has
been
developed.
This
protocol
enables
the
functionalization
both
activated
and
unactivated
alkenes,
in
directed
nondirected
manners.
Mono-,
di-,
trisubstituted
can
be
effectively
transformed.
Highly
diastereoselective
hydroalkylations
have
also
demonstrated.
The
method
provides
a
novel
approach
for
introducing
an
α-carbonyl
moiety
to
which
is
currently
inaccessible
by
existing
methods.
Preliminary
mechanistic
investigations
suggest
carbene-type
mechanism,
unusual
nickel
catalysis.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(5), С. 1245 - 1251
Опубликована: Янв. 1, 2023
Cyclopropylamine
synthesis:
using
halomethyl
radicals
as
the
CH
2
source,
photoredox-catalysed
cyclopropanation
of
N
-vinylimides
could
proceed
well,
giving
modular
access
to
1-
or
2-arylcyclopropylamines.
Chinese Journal of Organic Chemistry,
Год журнала:
2024,
Номер
44(2), С. 398 - 398
Опубликована: Янв. 1, 2024
The
structure
of
3-sulfenyl
indoles
widely
exists
in
many
drug
molecules
and
natural
product
molecules.Its
derivatives
have
extensive
biological
activities
such
as
antibacterial,
antiviral
anti-tumor,
are
also
important
intermediates
organic
synthesis
structural
units
synthesis.Therefore,
indole
compounds
great
application
value
the
field
medicine.The
research
its
method
has
become
one
current
hotspots.In
this
paper,
progress
recent
years
is
reviewed,
some
reaction
mechanisms
discussed.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(18), С. 2717 - 2727
Опубликована: Сен. 2, 2024
ConspectusThe
potent
reactivity
of
carbenes
and
nitrenes
has
been
traditionally
harnessed
by
the
employment
a
transition-metal
catalyst
in
which
metal
carbene/nitrene
intermediates
can
be
controlled
via
judicious
tuning
catalyst.
In
recent
years,
progress
made
this
research
area
unveiled
novel
strategies
to
directly
access
free
or
under
visible-light-mediated
conditions
without
necessity
for
stabilization
intermediate.
Such
photochemical
approaches
present
new
opportunities
leverage
orthogonal
reactions
with
classic
metal-catalyzed
transformations.In
Account,
we
describe
major
contributions
from
our
group
over
past
years
pushing
boundaries
light-mediated
carbene
nitrene
transfer
reactions.
first
section,
development
purely
singlet
chemistry
toward
methods
that
allow
triplet
will
dissected.
We
how
spin
state
reagents
provides
rich
array
synthetic
build
on
fundamentals
conservation.
lay
out
different
accessing
(i.e.,
electronic
stabilization,
sensitization
suitable
photocatalysts,
exploitation
geometric
features
these
intermediates),
followed
an
analysis
employed
distinct
chemistry.The
second
part
focuses
intermediates,
whereby
both
photocatalytic
are
analyzed
compared.
initiate
discussion
iminoiodinanes
as
precursors
presence
photocatalyst
two
result
fundamentally
nitrogen-based
intermediates.
While
radical
anion
is
formed
conditions,
generated
conditions.
commence
outline
basic
focus
reaction
substrates
containing
double
bonds.
Finally,
latest
developments
advanced
cycloaddition
beyond
aziridination
examined,
special
emphasis
relay
enable
Pauson-Khand-like
(2
+
2
1)
offers
convenient
high
value
bioisosteres
drug
discovery.The
work
spin-dependent
reactivities
insight
into
important
synthesis,
where
reactive
intermediate
dictate
outcome.
hope
may
inspire
others
widen
scope
applications
and/or
reactions,
furthermore,
anticipate
understandings
also
catalytic
systems
featuring
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 7, 2024
Cyclopropanes
are
not
only
privileged
motifs
in
many
natural
products,
agrochemicals,
and
pharmaceuticals,
but
also
highly
versatile
intermediates
synthetic
chemistry.
As
such,
great
effort
has
been
devoted
to
the
cyclopropane
construction.
However,
novel
catalytic
methods
for
cyclopropanation
with
two
abundant
substrates,
mild
conditions,
high
functional
group
tolerance,
broad
scope
still
desirable.
Herein,
we
report
an
intermolecular
electrocatalytic
of
alkenyl
trifluoroborates
methylene
compounds.
The
reaction
uses
simple
diphenyl
sulfide
as
electrocatalyst
under
base-free
conditions.
And
thus,
a
various
compounds
well
vinyltrifluoroborates
is
demonstrated,
including
styrenyl,
1,3-dienyl,
fluorosulfonyl,
base-sensitive
substrates.
Preliminary
mechanistic
studies
presented,
revealing
critical
role
boryl
substituent
facilitate
desired
pathway
water
hydrogen
atom
source.
