ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12225 - 12233
Опубликована: Авг. 1, 2024
Skipped
dienes
are
not
only
present
in
fatty
acid
primary
metabolites
and
natural
products
but
also
serve
as
reactive
intermediates
diverse
chemical
synthesis.
Despite
this,
the
regioselective
stereoselective
synthesis
of
skipped
remains
a
challenging
goal.
Strain
release
organic
molecules
is
powerful
tool
for
creating
complexity
under
mild
conditions.
The
reactivity
strained
bicyclo[1.1.0]butane
(BCB)
systems
mainly
dominated
by
transformations
relying
on
their
innate
electrophilic
reactivity.
Herein,
we
report
rare
example
carbene-type
BCB
system
based
rhodium–carbene
chemistry,
which
enables
highly
through
strain
release.
reaction
compatible
with
range
functional
groups
both
diazo
compounds
BCBs
could
be
applied
successfully
to
complex
structures,
providing
valuable
functionalizable
dienes.
introduced
during
served
synthetic
handles
downstream
manipulations.
high
stereoselectivity
observed
has
been
rationalized
DFT
calculations,
suggests
that
likely
proceeding
via
concerted
mechanism,
noncovalent
interactions
between
metallocarbene
control
exclusive
selectivity.
Chemistry - A European Journal,
Год журнала:
2020,
Номер
27(4), С. 1270 - 1281
Опубликована: Авг. 5, 2020
Abstract
Among
the
available
methods
to
increase
molecular
complexity,
sigmatropic
rearrangements
occupy
a
distinct
position
in
organic
synthesis.
Despite
being
known
for
over
century
rearrangement
reactions
of
ylides
via
carbene
transfer
reaction
have
only
recently
come
age.
Most
ylide
mediated
processes
involve
rupture
σ‐bond
and
formation
new
bond
between
π‐bond
negatively
charged
atom
followed
by
simultaneous
redistribution
π‐electrons.
This
minireview
describes
advances
this
research
area
made
recent
years,
which
now
opens
up
metal‐catalyzed
enantioselective
reactions,
metal‐free
photochemical
novel
pathways
that
can
be
accessed
intermediates.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(38), С. 13492 - 13498
Опубликована: Июль 23, 2019
Abstract
Catalytic
enantioselective
[2,3]
Stevens
and
Sommelet–Hauser
rearrangements
of
α‐diazo
pyrazoleamides
with
sulfides
were
achieved
by
utilizing
chiral
N
,
′‐dioxide/nickel(
II
)
complex
catalysts.
These
proceeded
well
under
mild
reaction
conditions,
providing
rapid
facile
access
to
a
series
functionalized
1,6‐dicarbonyls
or
sulfane‐substituted
phenylacetates
high
excellent
enantioselectivities.
The
catalytic
system
shows
stereocontrol,
discriminating
between
the
heterotopic
lone
pairs
sulfur
controlling
both
1,3‐proton
transfer
[2,3]‐σ
rearrangement.
Organic Letters,
Год журнала:
2019,
Номер
21(21), С. 8814 - 8818
Опубликована: Окт. 16, 2019
Cyclopropanation
reactions
of
carbenes
with
arenes
provide
a
straightforward
pathway
to
norcaradienes
or
cycloheptatrienes.
This
reaction
normally
requires
harsh
conditions
transition-metal
catalysts.
In
this
report,
we
describe
the
metal-free
visible-light
photolysis
aryl
diazoacetates
in
aromatic
solvents,
which
provides
access
norcaradiene
ring
system
highly
regio-
and
stereoselective
manner.
The
mild
approach
also
allow
chemoselective
cyclopropanation
substituted
without
competing
C-H
functionalization
reactions.
Chem,
Год журнала:
2020,
Номер
6(9), С. 2364 - 2381
Опубликована: Июль 22, 2020
Lewis
acidic
boranes
have
been
shown
to
be
effective
metal-free
catalysts
for
highly
selective
reactions
of
donor-acceptor
diazo
compounds
a
range
substrates.
The
α-aryl
α-diazoesters
with
nitrogen
heterocycles
indole
or
pyrrole
selectively
generate
C3
and
C2
C–H
insertion
products,
respectively,
in
good
excellent
yields
even
when
using
unprotected
indoles.
Alternatively,
benzofuran,
indene,
alkene
substrates
give
exclusively
cyclopropanated
products
α-diazoesters,
whereas
the
furans
lead
ring-opening.
Comprehensive
theoretical
calculations
used
explain
differing
reactivities
high
selectivities
these
reactions.
Overall,
this
work
demonstrates
catalytic
(hetero)cycles
alkenes.
This
simple,
mild
reaction
protocol
represents
an
alternative
commonly
precious
metal
systems
may
provide
future
applications
generation
biologically
active
compounds.
ChemistrySelect,
Год журнала:
2021,
Номер
6(4), С. 663 - 679
Опубликована: Янв. 25, 2021
Abstract
The
ever‐growing
interest
for
organoselenium
compounds
amongst
the
chemists
has
made
commendable
impact
in
field
of
medicinal
chemistry,
material
chemical
biology
and
biochemistry.
Researchers
have
progressively
contributed
development
over
years
which
been
periodically
reviewed.
On
similar
note,
this
review
attempts
at
providing
an
overview
recent
advances
chemistry
while
covering
their
catalytic
indulgence
different
transformational
approaches,
role
asymmetric
synthesis,
synthetic
approaches
steering
synthesis.
These
encompass
selenofunctionalization
and/or
cyclization,
electrochemical
selenylation,
bromolactonization,
[2,3]‐
or
[1,2]‐sigmatropic
rearrangement
reactions
among
others.
Herein,
we
focused
on
developed
past
three
that
not
covered
previously
reviewed
scientific
material.
With
knowledge
progress
covered,
could
contribute
towards
future
along
with
improvement
current
status.
Chemical Science,
Год журнала:
2022,
Номер
13(42), С. 12290 - 12308
Опубликована: Янв. 1, 2022
Catalytic
asymmetric
sigmatropic
rearrangements
induced
by
chiral
metal
catalysis
have
been
intensively
explored.
This
review
summarizes
recent
significant
advances,
mainly
involving
[3,3],
[2,3]
and
[1,3]-rearrangements.
Synlett,
Год журнала:
2019,
Номер
30(17), С. 1929 - 1934
Опубликована: Июнь 26, 2019
Carbenes
are
versatile,
highly
reactive
intermediates
with
great
importance
in
chemistry.
We
recently
reported
on
our
findings
safe
and
scalable
applications
of
hazardous
diazoacetonitrile
using
cheap
commercially
available
iron
catalysts
efficient
carbene
transfer
reactions,
ranging
from
cyclopropanation
towards
C–H
functionalization
reactions
for
the
synthesis
biologically
important
building
blocks.
More
lately,
we
uncovered
reactivity
diazoalkanes
under
photochemical
conditions
visible
light
were
able
to
demonstrate
a
variety
different,
metal-free
which
now
open
up
new
sustainable
ways
construction
small
functional
molecules.
1
Introduction
2
Iron-Catalyzed
Carbene
Transfer
Reactions
Diazoacetonitrile
3
Metal-free
Reaction
Visible
Light
4
Summary
Chemical Communications,
Год журнала:
2019,
Номер
56(4), С. 599 - 602
Опубликована: Дек. 3, 2019
Herein,
we
report
on
a
photochemical
three-component
reaction
of
aryldiazoacetates
with
NFSI
and
cyclic
ethers.
This
method
allows
the
introduction
both
fluorine
short
ether
sidechain
using
1,4-dioxane
as
solvent
in
high
yields
via
an
ylide
pathway
demonstrated
by
DFT
calculations
(26
examples,
up
to
99%
yield).
Chemical Communications,
Год журнала:
2019,
Номер
55(58), С. 8410 - 8413
Опубликована: Янв. 1, 2019
Benzyl
thioethers
undergo
rhodium(ii)
catalyzed
sigmatropic
rearrangement
reactions
with
aryldiazoacetates.
Depending
on
the
solvent
and
electronic
properties
of
sulfide,
intermediate
ylide
undergoes
either
[1,2]-
or
[2,3]-sigmatropic
in
high
yields.
