Bulletin of the Chemical Society of Japan,
Journal Year:
2024,
Volume and Issue:
97(11)
Published: Oct. 21, 2024
Abstract
The
replacement
of
C–H
bonds
with
more
stable
C–D
at
the
α-position
heteroatoms,
which
is
typical
metabolic
site
for
cytochrome
P450,
important
in
drug
discovery.
Recently,
we
have
developed
dn
(deuterated)-alkylated
sulfonium
salts
(1a-dn),
were
easily
prepared
by
deuteration
(H/D
exchange
reaction)
D2O
corresponding
alkyl
diphenylsulfonium
(1a),
as
electrophilic
dn-alkylating
reagents
(cation
sources).
Herein,
newly
report
an
improved
preparation
method
1a
and
one-pot
synthesis
dn-alkylated
compounds
via
subsequent
nucleophilic
substitution
under
basic
conditions.
Additionally,
dn-alkyl
thianthrenium
(1b-dn)
also
found
to
work
Furthermore,
1b-dn
served
radical
sources
photo-induced
reaction
conditions
Ir
photocatalyst,
Hantzsch
ester,
or
triphenylamine
obtain
various
regioselectively
deuterium-incorporated
compounds.
These
will
contribute
advance
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(46), P. 13690 - 13707
Published: Jan. 1, 2022
This
review
summarizes
the
synthesis
of
diverse
organothianthrenium
salts
from
various
precursors
and
their
applications
in
organic
to
forge
new
C–C,
C–H
C–heteroatom
bonds
by
C–S
bond
cleavage
with
different
mechanistic
considerations.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(36), P. 5343 - 5364
Published: Jan. 1, 2023
The
activation
and
transformation
of
organic
chemical
bonds
is
a
fundamental
scientific
problem.
In
the
past
several
decades,
C-S
bond
cleavage
for
construction
C-C
C-heteroatom
has
received
tremendous
attention
in
chemistry.
Although
significant
progress
been
made
field
transition
metal
strategies,
variety
novel
transition-metal-free
strategies
have
also
developed
using
halogenated
reagents,
oxidants,
acids,
bases.
Moreover,
photochemical
electrochemical
methods
to
achieve
organosulfur
compounds.
To
date,
however,
no
comprehensive
review
reported.
Therefore,
we
herein
provide
major
advances
compounds,
including
thioethers,
sulfoxides,
sulfones,
thioacetals,
sulfonium
salts,
sulfur
ylides.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(9), P. 6078 - 6144
Published: April 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(32), P. 5918 - 5923
Published: Aug. 5, 2022
An
attractive,
versatile,
and
operationally
simple,
visible-light-induced,
transition-metal-free,
photocatalyst-free,
oxidant-free
trifluoromethylation
has
been
demonstrated.
Triflic
anhydride
(Tf2O),
being
inexpensive
readily
available,
was
chosen
as
the
radical
trifluoromethyl
source.
Thianthrene
used
a
recyclable
Tf2O-activating
reagent,
high-yielding
scalable
reaction
achieved.
Density
functional
theory
mechanistic
studies
showed
that
free
homolytic
process
excited
by
visible
light
is
involved
in
this
reaction,
generating
key
intermediate.
Asian Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
11(10)
Published: Aug. 29, 2022
Abstract
In
the
early
days
of
synthetic
organic
chemistry
Hantzsch
esters
(HEs)
were
bio‐inspired
hydride
donors
and
often
used
for
reduction
C=X
(X=C,
N,
O)
bonds.
Recently,
it
has
been
proved
that
HEs
their
derivatives
(4‐Alkyl‐
or
acyl‐Hantzsch
esters)
serve
as
electron
donor,
proton
source,
hydrogen
atom
alkyl
acyl
radical
precursors
in
photoredox
catalysis.
Recently
was
found
excited‐state
also
identified
a
strong
photo
reductant
absence
photocatalyst
also,
donor
HE
forms
EDA‐complexes
with
molecules
triggers
SET
process
to
generate
carbon
entities.
This
minireview
focuses
on
recent
developments
where
act
synthesis,
special
focus
reaction
mechanisms.
We
hope
this
review
will
help
further
development
radical‐based
transformations
external
photocatalysts.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4786 - 4827
Published: Jan. 1, 2024
This
review
summarizes
structural
and
synthetic
aspects
of
heterocyclic
molecules
incorporating
an
atom
a
hypervalent
main-group
element.
The
higher
thermal
stability
heterocycles,
as
compared
to
their
acyclic
analogs,
adds
special
feature
chemistry.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(17), P. 9371 - 9377
Published: Jan. 1, 2024
Defluorinative
alkylation
and
arylation
between
thianthrenium
salts
α-trifluoromethyl
alkene
to
afford
gem
-difluoroolefins
by
easily
recycling
thianthrene
under
visible
light
irradiation
free
of
metal
photocatalyst.
Chinese Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
42(12), P. 4037 - 4037
Published: Jan. 1, 2022
Sulfonium
salts
are
one
of
the
most
important
class
organosulfur
(IV)
compounds
which
have
a
positive
charge
on
sulfur
center
with
three
C-S
bonds.Because
their
bench-stable,
easy
synthesis,
broad
structural
diversity,
and
rich
reactivity,
sulfonium
playing
significant
role
in
synthetic
chemistry.In
recent
years,
visible-light
promoted
photoredox
catalysis
is
rapidly
developing
into
powerful
tool
for
organic
synthesis.In
this
paper,
advances
different
radical
type
reactions
induced
by
visible
light
summarized.The
formation
C-C
bond
C-X
(X＝B,
N,
O,
S,
Se,
Te,
F,
Cl,
I)
bonds
introduced,
applicable
scope
mechanism
some
also
discussed.Keywords
chemistry;
salt;
light;
free
reaction
有机硫化合物在合成化学、生物医学和功能有机材
料领域扮演着极其重要的角色
[1]
.据统计结果显示,
美
国销量排名前
200
位的药品中,
有
24.8%含有硫元素
[2]
.硫原子与同族的氧原子相比,
其半径更大、电负性更低,
使得硫的外电子层更易于接受或提供电子,
显示出独特
的反应活性,
而硫鎓盐是中心硫原子与三个取代基相连
的带正电的有机硫化合物(通式为[R
3
S]
＋
X
-).与同族氧
鎓盐相比,
硫鎓盐结构更加多样、热力学稳定性更强、
更易于合成、后处理更加简便
[3]
.常见的硫鎓盐的合成方法如
Scheme
1
所示
[4]
:
(a)通
过二卤代烃与硫醇的亲核取代反应,
该方法制备硫鎓盐
操作简便,
结晶度好且稳定性高,
但主要局限于五元环
和六元环状硫鎓盐的制备.(b)采用硫醚和烷基卤化物通
过分子间亲核取代反应制备硫鎓盐,
该方法是目前应用
有机化学
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(20), P. 4388 - 4393
Published: May 16, 2024
Herein,
a
photoredox-driven
practical
protocol
for
fluorinated
alkene
synthesis
using
easily
accessible
and
modular
thianthrenium
salts
with
electron-withdrawing
alkynes
or
propargyl
alcohols
is
reported.
Vinyl
radical
intermediates,
formed
by
the
reaction
between
alkyl
trifluoromethyl
electronically
diverse
alkynes,
can
mediate
key
1,5-HAT
process
of
regioselective
C(sp3)–H
fluorination
vinylation.
This
provides
straightforward
access
to
structurally
trifluoromethyl-
distally
fluoro-functionalized
products
in
21–79%
yields
broad
substrate
range
under
mild
photocatalytic
conditions.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(18), P. 3789 - 3793
Published: Jan. 1, 2023
We
developed
an
efficient
palladium-catalyzed
fluorosulfonylation
reaction
of
aryl
thianthrenium
salts
to
smoothly
prepare
various
sulfonyl
fluorides
using
cheap
Na2S2O4
as
a
convenient
source
in
combination
with
N-fluorobenzenesulfonimide
(NFSI)
ideal
fluorine
under
mild
reduction
conditions.
A
one-pot
synthesis
starting
from
arenes
was
established
well
without
the
need
for
separating
salts.
The
practicality
this
protocol
demonstrated
by
gram-scale
synthesis,
derivatization
reactions,
and
excellent
yields.
