Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 2, 2024
Abstract
The
efficient
construction
of
chalcogen‐atom‐based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three‐component
or
four‐component
reaction,
through
Se−S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti‐inflammatory
toward
IL‐1β
low
cytotoxicity.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3664 - 3674
Published: Feb. 21, 2024
Regioselective
1,2-dichalcogenation
of
alkenes
has
attracted
significant
attention
in
modern
organic
synthetic
chemistry.
While
there
are
a
plethora
methods
to
access
alkene
dichalcogenated
architectures,
sulfonylsulfination
is
extremely
challenging
due
the
inherent
characteristics
sulfur
atom.
Herein,
multicomponent
fragment
coupling
alkenes,
sulfinates,
and
DABSO
was
developed
construct
densely
functionalized
sulfonylsulfinated
products,
which
otherwise
access,
with
broad
substrate
scope
group
tolerance
under
mild
operationally
simple
conditions,
using
an
inexpensive
100–1000
ppm
photocatalyst.
In
addition,
protocol
applied
late-stage
functionalization
complex
molecules,
obtained
products
were
converted
into
diverse
downstream
transformations
demonstrate
their
potential.
Experimental
theoretical
mechanistic
investigations
suggest
that
these
reactions
proceed
through
sequential
sulfonyl
sulfinyl
oxygen
radical
mutual
radical–polar
crossover
coupling.
This
strategy
provides
previously
inaccessible
good-to-high
regio-
stereoselectivity,
along
opening
up
unexplored
directions.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(23), P. 6684 - 6707
Published: Jan. 1, 2022
This
review
systematically
summarizes
the
recent
developments
for
constructing
sulfur
compounds
from
electrophiles,
and
mechanism
mainly
involved
thirranium
ions,
ylides,
C–S
cross
coupling
electrophilic
substitution.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(7), P. 4656 - 4666
Published: March 22, 2023
A
visible-light-induced
enantioselective
free
carbene
transfer
reaction
of
α-diazoesters
with
1,3-diketones
is
established
by
utilizing
a
chiral
bifunctional
guanidine-amide
organocatalyst.
Selective
insertion
into
the
C–C
or
C–H
bonds
1,3-diketone
could
be
achieved
bearing
different
steric
hindrances.
The
transformations
enable
preparation
series
1,4-diketones
quaternary
carbon
center
2-substituted-1,3-diketones
in
good
enantioselectivities.
On
basis
control
experiments
and
DFT
calculation,
stepwise
triplet
coupling
pathway
suggested.
possible
mechanism
proposed
to
explain
origin
high
enantioselectivities
via
hydrogen-bonds
electrostatic
interactions
catalyst.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(19), P. 4972 - 5027
Published: Jan. 1, 2023
This
review
comprehensively
summarizes
the
dichalcogenative
functionalization
of
unsaturated
compounds
over
past
decade.
The
scopes,
limitations
and
detailed
reaction
mechanisms
are
also
discussed.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 5, 2024
The
[1,2]-
and
[2,3]-Stevens
rearrangements
are
one
of
the
most
fascinating
chemical
bond
reorganization
strategies
in
organic
chemistry,
they
have
been
demonstrated
a
wide
range
applications,
representing
fundamental
reaction
tactic
for
synthesis
nitrogen
compounds
community.
However,
their
applicabilities
limited
by
scarcity
efficient,
general,
straightforward
methods
generating
ammonium
ylides.
Herein,
we
report
general
difluorocarbene-induced
tertiary
amine-involved
stemmed
from
situ
generated
difluoromethyl
ylides,
which
allows
versatile
amines
bearing
either
allyl,
benzyl,
or
propargyl
groups,
resulting
corresponding
products
under
same
conditions
with
way.
Broad
substrate
scope,
simple
operation,
mild
late-stage
modification
natural
highlight
advantages
this
strategy,
meanwhile,
rearrangement
is
believed
to
bring
opportunities
transformations
ylides
assembly
valuable
amino
acids.
This
will
further
enrich
repertoire
difluorocarbene
species,
facilitate
development
reactions
involving
salts,
provide
an
avenue
type
reactions.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(32)
Published: June 15, 2023
We
realized
a
highly
efficient
formal
[1,2]-sigmatropic
rearrangement
of
ammonium
ylides
generated
from
3-methylene-azetidines
and
α-diazo
pyrazoamides.
The
employ
readily
available
chiral
cobalt(II)
complex
N,N'-dioxide
enabled
the
ring-expansion
azetidines,
affording
variety
quaternary
prolineamide
derivatives
with
excellent
yield
(up
to
99
%)
enantioselectivity
%
ee)
under
mild
reaction
condition.
For
ylides,
installation
pyrazoamide
group
as
masked
brick
build
scaffolds
proved
successful.
enantioselective
ring
expansion
process
was
elucidated
by
DFT
calculations.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(21), P. 3107 - 3110
Published: Jan. 1, 2023
The
Sc(III)-catalyzed
[2,3]-sigmatropic
rearrangement
of
sulfonium
ylides
derived
from
azoalkenes
has
been
established.
Owing
to
the
absence
a
carbenoid
intermediate,
this
protocol
represents
first
non-carbenoid
variant
Doyle-Kirmse
reaction.
Under
mild
conditions,
variety
tertiary
thioethers
have
readily
prepared
in
good
excellent
yields.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
A
properly
designed
chiral
copper
complex
with
a
hybrid
tridentate
ligand
enables
photocatalytic
asymmetric
cyanoalkylalkynylation
of
olefins
using
cycloketone
oxime
esters
as
the
precursors.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 2, 2024
The
efficient
construction
of
chalcogen-atom-based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three-component
or
four-component
reaction,
through
Se-S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti-inflammatory
toward
IL-1β
low
cytotoxicity.
Synthesis,
Journal Year:
2023,
Volume and Issue:
55(14), P. 2118 - 2127
Published: March 8, 2023
Abstract
The
[1,2]-Stevens
rearrangement
is
a
widely
used
transformation
in
synthetic
organic
chemistry.
However,
enantioselective
versions
are
relatively
limited
and
most
of
them
rely
on
substrate-induced
methodologies.
In
recent
years,
metal
carbene
chemistry
has
been
extensively
investigated,
the
related
asymmetric
experienced
rapid
development
by
employing
ylide
intermediates
generated
from
reaction
carbenes
with
heteroatoms.
This
review
summarizes
advances
[1,2]-Stevens-type
via
presenting
their
product
diversity,
selectivity,
mechanistic
rationale,
which
organized
based
mode
chirality
control.
1
Introduction
2
Substrate-Induced
Asymmetric
[1,2]-Stevens-Type
Rearrangement
3
Catalyst-Controlled
4
Conclusion
Outlook
