Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(19), P. 4071 - 4076
Published: May 2, 2024
An
electrochemical
oxidative
difunctionalization
of
diazo
compounds
with
diselenides
and
nucleophiles
has
been
developed.
This
innovative
approach
yields
a
diverse
array
selenium-containing
pyrazole
esters
alkoxy
esters,
overcoming
the
limitations
traditional
synthesis
methods.
Remarkably,
various
nucleophiles,
including
acids,
alcohols,
pyrazoles,
can
be
seamlessly
incorporated.
Notably,
this
protocol
boasts
high
atom
efficiency,
excellent
functional
group
tolerance,
good
efficiency
operates
under
transition
metal-
oxidant-free
conditions,
distinguishing
it
in
field.
Chemistry - A European Journal,
Journal Year:
2020,
Volume and Issue:
27(4), P. 1270 - 1281
Published: Aug. 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,
Journal Year:
2019,
Volume and Issue:
58(38), P. 13492 - 13498
Published: July 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,
Journal Year:
2019,
Volume and Issue:
21(21), P. 8814 - 8818
Published: Oct. 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,
Journal Year:
2020,
Volume and Issue:
6(9), P. 2364 - 2381
Published: July 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,
Journal Year:
2021,
Volume and Issue:
6(4), P. 663 - 679
Published: Jan. 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,
Journal Year:
2022,
Volume and Issue:
13(42), P. 12290 - 12308
Published: Jan. 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,
Journal Year:
2019,
Volume and Issue:
30(17), P. 1929 - 1934
Published: June 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,
Journal Year:
2019,
Volume and Issue:
56(4), P. 599 - 602
Published: Dec. 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,
Journal Year:
2019,
Volume and Issue:
55(58), P. 8410 - 8413
Published: Jan. 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.
