The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(21), С. 15335 - 15349
Опубликована: Окт. 24, 2023
We
report
the
first
example
of
B(C6F5)3-catalyzed
O-H
insertion
reaction
sulfoxonium
ylides
and
carboxylic
acids,
achieving
efficient
construction
diester
moieties
under
metal-free
condition.
This
protocol
is
characterized
by
broad
substrate
tolerance,
particularly
for
various
phenylacetic
good
compatibility
with
water/air
condition,
which
superior
to
most
other
methods.
Chemical Science,
Год журнала:
2021,
Номер
13(5), С. 1192 - 1209
Опубликована: Дек. 8, 2021
Sulfoxonium
ylides
are
important
surrogates
for
diazo
compounds,
and
their
use
in
industry
as
safer
alternatives
has
been
evaluated
during
recent
years.
Beyond
the
known
classical
transformations,
these
have
also
used
a
surprising
plethora
of
novel
intrinsic
chemical
reactions,
especially
Bench
stability
handling
an
advantage
this
class
organosulfur
molecules.
Despite
this,
efficient
asymmetric
specifically
catalytic
enantioselective
versions,
only
recently
reported,
there
specific
reasons
this.
This
perspective
article
covers
topic
from
first
studies
up
to
latest
advances,
giving
personal
perspectives
showing
main
challenges
area
coming
Chemical Science,
Год журнала:
2022,
Номер
14(4), С. 843 - 848
Опубликована: Ноя. 29, 2022
While
asymmetric
insertion
of
metal
carbenes
into
H-X
(X
=
C,
N,
O,
etc.)
bonds
has
been
well-established,
control
over
free
is
challenging
due
to
the
presence
strong
background
reactions
and
lack
any
anchor
for
a
catalyst
interaction.
Here
we
have
achieved
first
photo-induced
metal-free
bond
this
type.
With
visible
light
used
as
promoter
chiral
phosphoric
acid
catalyst,
α-diazoesters
aryl
amines
underwent
smooth
N-H
form
enantioenriched
α-aminoesters
with
high
efficiency
good
enantioselectivity
under
mild
conditions.
Key
success
was
use
DMSO
an
additive,
which
served
rapidly
capture
highly
reactive
carbene
intermediate
domesticated
sulfoxonium
ylide.
Organic Letters,
Год журнала:
2023,
Номер
25(23), С. 4286 - 4291
Опубликована: Июнь 2, 2023
Two
categories
of
tetrasubstituted
phenols
were
prepared
via
the
cycloaddition
reaction
vinyl
sulfoxonnium
ylides
with
cyclopropenones
in
a
switchable
manner.
Copper
carbenoid
was
proposed
as
active
intermediate
process
2,3,4,5-tetrasubstituted
formation,
while
2,3,5,6-tetrasubstituted
generated
direct
[3
+
3]
annulation
under
metal-free
conditions.
Further
synthetic
applications
also
demonstrated.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2779 - 2788
Опубликована: Янв. 18, 2024
Catalytic
enantioselective
α-chlorination
of
ketones
is
a
highly
desirable
process.
Different
from
the
conventional
approaches
that
employ
corrosive
electrophilic
chlorination
reagents,
process
disclosed
here
employs
nucleophilic
chloride,
aqueous
NaCl
solution,
and
even
seawater,
as
green
inexpensive
chlorine
sources.
This
mechanistically
distinct
electronically
opposite
approach
provides
facile
access
to
diverse
enantioenriched
acyclic
α-chloro
are
less
straightforward
by
approaches.
With
chiral
thiourea
catalyst,
range
racemic
α-keto
sulfonium
salts
underwent
enantioconvergent
carbon–chlorine
bond
formation
with
high
efficiency
excellent
enantioselectivity
under
mild
conditions.
The
motif
plays
crucial
triple
role
permitting
smooth
dynamic
kinetic
resolution
take
place
via
anion
binding
mechanism
in
well-designed
phase-transfer
system.
protocol
represents
new
general
platform
for
asymmetric
α-functionalization
carbonyl
compounds.
JACS Au,
Год журнала:
2023,
Номер
3(1), С. 252 - 260
Опубликована: Янв. 3, 2023
Herein,
we
describe
the
development
of
a
new
strategy
for
synthesis
unsaturated
oligoesters
via
sequential
metal-
and
reagent-free
insertion
vinyl
sulfoxonium
ylides
into
O-H
bond
carboxylic
acid.
Like
two
directional
coupling
amino
acids
(N-
to
C-terminal
C-
N-terminal)
in
peptide
synthesis,
present
approach
offers
both
directions
synthesize
oligoesters.
The
addition
ylide
(acid
iteration
sequence)
one
direction
(ylide
another
yield
(Z)-configured
To
perform
this
iteration,
have
developed
highly
regioselective
X-H
(X
=
O,
N,
C,
S,
halogen)
acids,
thiols,
phenols,
amines,
indoles,
halogen
under
metal-free
reaction
conditions.
is
applied
broad
range
substrates
(>50
examples,
up
99%
yield)
eight
iterative
sequences.
Mechanistic
studies
suggest
that
rate-limiting
step
depends
on
type
insertion.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(34)
Опубликована: Июнь 17, 2022
A
rhodium(I)-diene
catalyzed
highly
enantioselective
C(sp2
)-H
functionalization
of
simple
unprotected
indoles,
pyrroles,
and
their
common
analogues
such
as
furans,
thiophenes,
benzofurans
with
arylvinyldiazoesters
has
been
developed
for
the
first
time.
This
transformation
features
unusual
site-selectivity
exclusively
at
vinyl
terminus
arylvinylcarbene
enables
a
reliable
rapid
synthetic
protocol
to
access
distinctive
class
diarylmethine-bearing
α,β-unsaturated
esters
containing
one
or
two
heteroarene-attached
tertiary
carbon
stereocenter
in
high
yields
excellent
enantioselectivities
under
mild
reaction
conditions.
Mechanistic
studies
DFT
calculations
suggest
that,
compared
aniline
substrate,
more
electron-rich
indole
substrate
lowers
C-C
addition
barrier
alters
rate-determining
step
reductive
elimination,
leading
different
isotope
effect.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Ноя. 3, 2022
The
development
of
novel
methodologies
for
the
introduction
sulfoxonium
group
under
mild
conditions
is
appealing
but
remains
underexplored.
Herein
we
report
synthesis
a
class
hypervalent
iodine
reagents
with
transferrable
group.
These
compounds
enable
mixed
iodonium-sulfoxonium
ylide
reactivity.
well-defined
are
examined
in
visible-light-promoted
cyclization
reactions
wide
range
unsaturated
bonds
including
alkenes,
alkynes,
nitriles,
and
allenes.
Two
distinct
pathways
identified,
which
controlled
by
substituent
bond.
cycloaddition
protocol
features
simple
operation,
reaction
conditions,
excellent
functional
tolerance,
affording
broad
sulfoxonium-containing
cyclic
structures
moderate
to
yields.
Furthermore,
sufoxonium
product
can
be
transformed
into
diverse
groups
structural
motifs
via
single
electron
transfer
transition-metal
catalysis.
Catalysts,
Год журнала:
2023,
Номер
13(4), С. 689 - 689
Опубликована: Март 31, 2023
Sulfur
ylides
are
an
important
class
of
organic
compounds
due
to
their
ability
perform
many
different
transformations
that
can
give
diverse
and
interesting
products
with
a
high
degree
complexity.
Although
metal-catalyzed
frequent
in
this
compounds,
organocatalyzed
remain
scarce.
From
initial
works,
review
aims
show
from
sulfur
ylides,
involving
cyclopropanation
formal
N–H,
S–H,
C–H
insertion
reactions,
including
enantioselective
versions.
The
proposed
mechanisms
the
modes
activation
these
organocatalysts
will
be
covered.
Furthermore,
advances
area
potential
challenges
circumvented
near
future
also
discussed.
Abstract
The
study
of
the
reactivity
cyclic
sulfoxonium
ylides
has
been
so
far
neglected,
in
particular
for
reactions
that
forms
carbon‐carbon
bond
at
ylide
carbon
atom.
Herein,
we
describe
synthesis
by
palladium‐catalyzed
intramolecular
arylation
and
these
C3‐alkylation
indoles
presence
either
an
acid
catalyst
or
iridium
catalyst.
This
revealed
catalysis
is
only
efficient
which
tether
a
six‐membered
lactone,
whereas
was
better
suited
to
reaction
five‐membered
ring
ketone
lactone.
observed
chemospecificity
might
be
due
relative
basicity
under
steric
hindrance
around
carbene
intermediate
when
conducted
with
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(15), С. 9815 - 9828
Опубликована: Июль 15, 2022
In
this
paper,
a
selective
synthesis
of
indolo[1,2-c]quinazolines
and
indolo[3,2-c]quinolines
through
the
cascade
reactions
2-(1H-indol-2-yl)anilines
with
sulfoxonium
ylides
is
presented.
The
formation
products
involves
generation
carbene
species
from
ylide
its
N–H
bond
insertion
reaction
2-(1H-indol-2-yl)aniline
followed
by
deoxygenative
imine
formation,
intramolecular
N–
or
C–
nucleophilic
addition
aromatization.
This
switchable
was
condition-dependent.
presence
K2CO3
in
CH3CN,
mainly
furnished
indolo[1,2-c]quinazolines.
HOAc
dioxane,
it
selectively
afforded
indolo[3,2-c]quinolines.
addition,
direct
C–H/N–H
functionalization
obtained
provides
convenient
access
to
polycyclic
heteroaromatic
compounds.
These
novel
protocols
have
advantages
such
as
readily
accessible
substrates,
easily
tunable
selectivity,
good
compatibility
diverse
functional
groups,
use
air
cost-free
sustainable
oxidant.