The Chemical Record,
Journal Year:
2018,
Volume and Issue:
18(11), P. 1548 - 1559
Published: May 29, 2018
Abstract
Cu(I)‐catalyzed
reaction
of
diazo
compounds
generates
a
Cu(I)‐carbene
intermediate
that
undergoes
diverse
transformations.
In
the
past
few
years,
(or
their
precursor
N
‐tosylhydrazones)
have
been
established
as
cross‐coupling
partners
under
transition‐metal
catalysis,
affording
various
organic
compounds.
Particularly
breakthrough
has
made
in
allene
synthesis
by
carbene
coupling
with
terminal
alkynes.
Moreover,
alkynes
tandem
cyclization/coupling
to
afford
cyclic
This
review
article
summarizes
most
recent
developments
based
on
reactions
and
utilization
intermediates
reactions.
Chemical Science,
Journal Year:
2019,
Volume and Issue:
10(43), P. 10129 - 10134
Published: Jan. 1, 2019
We
have
shown
light
mediated
ring-expansion
reactions
of
4-membered
ring
heterocycles.
The
reaction
proceeds
via
a
diradical
mechanism
and
bond
length
play
key
role
in
the
stereodetermining
step.
Chemical Communications,
Journal Year:
2019,
Volume and Issue:
55(33), P. 4881 - 4884
Published: Jan. 1, 2019
The
photolysis
of
donor–acceptor
diazoalkanes
in
the
presence
propargylic
alcohols
furnishes
valuable,
sterically
demanding
tetra-substituted
cyclopropenes
high
yield
under
metal-free
conditions.
Chemistry - A European Journal,
Journal Year:
2019,
Volume and Issue:
25(27), P. 6703 - 6706
Published: March 28, 2019
Abstract
Sigmatropic
rearrangement
reactions
constitute
one
of
the
most
fundamental
carbenes.
While
state‐of‐the‐art
synthetic
methods
require
use
expensive
precious
metal
catalysts,
application
visible
light
for
photolysis
α‐aryldiazoacetates
is
much
less
investigated
and
provides
an
operationally
simple
entry
to
carbenes
under
mild
reaction
conditions.
Herein,
we
report
on
blue‐light
induced
sigmatropic
sulfur
compounds
with
α‐aryldiazoacetates.
This
process,
depending
substitution
pattern
sulfide,
opens
up
formal
insertion
into
S−N,
S−C,
or
C−H
bonds.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
61(7)
Published: Dec. 14, 2021
Here,
we
report
a
copper-catalyzed
asymmetric
cascade
cyclization/[1,2]-Stevens-type
rearrangement
via
non-diazo
approach,
leading
to
the
practical
and
atom-economic
assembly
of
various
valuable
chiral
chromeno[3,4-c]pyrroles
bearing
quaternary
carbon
stereocenter
in
generally
moderate
good
yields
with
wide
substrate
scope
excellent
enantioselectivities
(up
99
%
ee).
Importantly,
this
protocol
not
only
represents
first
example
catalytic
[1,2]-Stevens-type
based
on
alkynes
but
also
constitutes
formal
carbene
insertion
into
Si-O
bond.
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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(10)
Published: Jan. 14, 2023
[2,3]-Sigmatropic
rearrangement
reaction
involving
sulfonium
ylide
(Doyle-Kirmse
reaction)
generated
from
metal
carbenes
represents
one
of
the
powerful
methods
for
construction
C(sp3
)-S
and
C-C
bonds.
Although
significant
advances
have
been
achieved,
asymmetric
versions
via
generation
ylides
rarely
reported
to
date,
they
so
far
limited
diazo
compounds
as
carbene
precursors.
Here,
we
describe
a
copper-catalyzed
enantioselective
Doyle-Kirmse
azide-ynamide
cyclization,
leading
practical
divergent
assembly
an
array
chiral
[1,4]thiazino[3,2-b]indoles
bearing
quaternary
carbon
stereocenter
in
generally
moderate
excellent
yields
enantioselectivities.
Importantly,
this
protocol
unique
catalytic
non-diazo
approach
unprecedented
[2,3]-sigmatropic
α-imino
carbenes.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 30, 2025
The
complicated
mechanism
makes
the
regiodivergent
rearrangement
of
ammonium
ylide
seem
to
be
out
reach.
Herein,
we
reported
a
gramine
well
controlled
by
substituents.
Density
functional
theory
studies
reveal
that
with
more
steric
hindrance
substituent
2-diazo-2-arylacetate
goes
through
stepwise
yield
both
kinetically
and
thermodynamically
preferred
[1,2]-rearrangement
product.
In
contrast,
less
ethyl
diazoacetate
concerted
generate
[2,3]-rearrangement
product,
which
is
favored
as
result
release
ring
strain
in
transition
state.
This
study
would
open
up
avenues
grasp
ylide,
will
promote
application
skeletal
editing
synthesis
complex
natural
products.
Chemical Communications,
Journal Year:
2017,
Volume and Issue:
53(49), P. 6577 - 6580
Published: Jan. 1, 2017
Slow
addition
of
sodium
nitrite
allows
the
in
situ
preparation
highly
explosive
diazo
compounds
and
enables
their
safe
scalable
application
iron
catalyzed
rearrangement
reactions
allylic
propargylic
sulfides.
With
catalyst
loadings
as
low
0.1
mol%
an
effective
entry
into
α-mercapto-nitriles,
α-mercapto-esters
α-trifluoromethyl-sulfides
on
a
gram-scale
is
achieved.
Organic Letters,
Journal Year:
2018,
Volume and Issue:
20(22), P. 7206 - 7211
Published: Oct. 26, 2018
A
general,
mild,
and
versatile
synthesis
of
the
challenging
α-aryl-β-ketosulfoxonium
ylides
has
been
developed
for
first
time,
substituting
traditional
methods
starting
from
diazo
compounds.
The
arylation
easily
accessible
β-ketosulfoxonium
using
aryne
chemistry
allowed
preparation
a
large
scope
pro-chiral
in
very
good
yields
(40
examples;
up
to
85%).
As
applications,
these
were
smoothly
converted
into
α-aryl
ketones
after
desulfurization
(up
98%)
as
well
other
important
derivatives.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(10), P. 3653 - 3657
Published: April 29, 2019
The
rearrangement
of
selenium
ylides
is
even
today
almost
unexplored,
although
it
would
provide
access
to
important
organoselenium
compounds
with
broad
downstream
applications.
In
this
report,
the
first
systematic
study
sigmatropic
reactions
using
a
simple
rhodium
catalyst
loadings
as
low
0.01
mol
%
described.
Selenium
oxide
pyrolysis
products
gives
1,1-disubstituted
butadienes.
