Encyclopedia of Reagents for Organic Synthesis,
Год журнала:
2024,
Номер
unknown, С. 1 - 6
Опубликована: Апрель 18, 2024
image
A
[
195072‐48‐1
]
C
19
H
13
F
3
O
S
(MW
442.48)
InChI
=
1S/C18H13S2.CHF3O3S/c1‐2‐8‐14(9‐3‐1)20‐17‐12‐6‐4‐10‐15(17)19‐16‐11‐5‐7‐13‐18(16)20;2‐1(3,4)8(5,6)7/h1‐13H;(H,5,6,7)/q+1;/p‐1
InChiKey
ILICKJZOLUIMMN‐UHFFFAOYSA‐M
B
2839478‐51‐0
20
14
ClF
4
506.95)
1S/C19H14ClOS2.CHF3O3S/c1‐21‐15‐11‐10‐13(12‐14(15)20)23‐18‐8‐4‐2‐6‐16(18)22‐17‐7‐3‐5‐9‐19(17)23;2‐1(3,4)8(5,6)7/h2‐12H,1H3;(H,5,6,7)/q+1;/p‐1
UHXRBIHFIKXURP‐UHFFFAOYSA‐M
2786722‐96‐9
12
6
510.48)
1S/C19H12F3S2.CHF3O3S/c20‐19(21,22)13‐9‐11‐14(12‐10‐13)24‐17‐7‐3‐1‐5‐15(17)23‐16‐6‐2‐4‐8‐18(16)24;2‐1(3,4)8(5,6)7/h1‐12H;(H,5,6,7)/q+1;/p‐1
UEAVFAKSNUECER‐UHFFFAOYSA‐M
D
2786723‐55‐3
18
NO
443.47)
1S/C17H12NS2.CHF3O3S/c1‐3‐7‐16‐14(5‐1)19‐15‐6‐2‐4‐8‐17(15)20(16)13‐9‐11‐18‐12‐10‐13;2‐1(3,4)8(5,6)7/h1‐12H;(H,5,6,7)/q+1;/p‐1
SRMXRMTYQFMLCQ‐UHFFFAOYSA‐M
(reagents
used
as
an
aryl
pseudohalide
in
transition‐metal
catalyzed,
transition
metal‐free,
and
photochemical
reactions)
Physical
Data
:
mp
202.8–204.7
°C.
1
159.2–162.7
2
(Not
reported).
A–D
Solubility
soluble
acetonitrile
dichloromethane.
–
Form
Supplied
not
commercially
available;
free‐flowing
solids
prepared
by
literature
procedures.
3–5
Analysis
of
Reagent
Purity
NMR.
Purification
trituration
from
dichloromethane
using
diethyl
ether
or
hexanes;
silica
gel
chromatography
(eluting
with
DCM:MeOH).
Handling,
Storage,
Precautions
stable
under
ambient
conditions
for
extended
periods
time.
Can
be
weighed
normal
atmosphere
stored
a
vial
air.
Preparative
Methods
(From
simple
arenes)
Treatment
thianthrene
‐oxide
(TTSO)
trifluoroacetic
anhydride
(TFAA)
triflic
acid
(TfOH)
the
presence
desired
arene
at
0
After
addition
all
reagents,
reactions
are
typically
allowed
to
stir
between
h
depending
on
substrate.
Alternatively,
treatment
TTSO
(Tf
O)
−40
3,5
completion,
purple
reaction
is
quenched
methanol
generate
colorless/yellow
solution.
The
crude
mixture
concentrated
reduced
pressure
residue
triturated
afford
solid
which
isolated
filtration.
arylboronic
acids)
thianthrene,
copper(II)
triflate
water
nitrogen
100
°C
h.
aqueous
workup,
Chemical Science,
Год журнала:
2022,
Номер
13(46), С. 13690 - 13707
Опубликована: Янв. 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.
ACS Catalysis,
Год журнала:
2023,
Номер
13(17), С. 11580 - 11588
Опубликована: Авг. 18, 2023
Despite
the
frequent
occurrence
of
sulfonamides
in
contemporary
pharmaceuticals
and
agrochemicals,
synthesis
these
compounds
is
limited
by
availability
preexisting
sulfur
functionality,
amine
nucleophilicity,
functional
group
compatibility.
Herein,
we
report
use
synergetic
photoredox
copper
catalysis
to
synthesize
from
a
variety
aryl
radical
precursors,
readily
available
amines,
dioxide
source
air
at
room
temperature.
The
reactions
proceeded
smoothly
with
various
electron-rich
electron-deficient
amines
generate
single-step
process.
Oxygen
was
deemed
be
essential
for
both
catalytic
cycles,
acting
as
catalyst.
Experimental
studies,
including
electron
paramagnetic
resonance
spectroscopy,
provided
insights
into
possible
mechanism.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(43)
Опубликована: Сен. 13, 2023
Abstract
The
utilization
of
aryl
radicals
as
open‐shelled
intermediates
has
become
an
essential
tool
for
both
conventional
and
state‐of‐the‐art
synthetic
chemistry.
However,
the
current
methods
generating
are
still
inefficient,
greatly
impeding
their
practical
applications.
Encouragingly,
sulfonium
salts
have
emerged
appealing
sources
a
wide
range
transformations
aimed
at
creating
novel
chemical
bonds
driven
by
distinctive
structural
attributes
tendencies.
This
review
primarily
focuses
on
specific
reaction
mechanisms
underlying
cleavage
C−S
in
salts,
leading
to
generation
corresponding
within
diverse
conditions.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 5227 - 5235
Опубликована: Март 21, 2024
Sulfonamides
are
prominently
featured
in
organic
synthesis
and
medicinal
chemistry.
Yet,
a
general
synthetic
platform
for
the
modular
construction
of
aryl
sulfonamides
remains
elusive.
Herein,
metal-free
photoredox-catalyzed
three-component
via
an
sulfonyl
ammonium
salt
intermediate,
which
was
generated
situ
SET
event,
has
been
established.
A
variety
structurally
diverse
primary,
secondary,
tertiary
were
synthesized
rapidly
from
abundant
amines
or
sodium
azide
under
mild
conditions.
Notably,
primary
aliphatic
amine,
challenging
Cu-catalyzed
protocols,
worked
well
this
approach.
Moreover,
fluoride
can
be
accessed
smoothly
as
well,
using
potassium
hydrogen
nucleophile.
The
potential
utility
conversion
is
demonstrated
facile
three
bioactive
drug
compounds.
Preliminary
mechanistic
studies
have
revealed
that
radical
key
intermediates
mechanistically
innovative
methodology.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(9), С. 4786 - 4827
Опубликована: Янв. 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.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2344 - 2351
Опубликована: Апрель 5, 2024
Abstract
A
process
for
the
synthesis
of
aryl
thioglycosides
from
thianthrenium
salts
and
1‐thiosugars
is
achieved
by
copper(I)‐mediated,
photoredox‐catalyzed
reactions.
The
desired
products
could
be
obtained
in
32%
to
78%
yield
after
irradiation
with
34
W
blue
light
at
room
temperature.
Various
functional
groups,
especially
including
halogen
were
well
tolerated
under
standard
reaction
conditions.
This
strategy
differs
conceptually
all
previous
S
‐glycosylations
that
thiosugar
functionality
incorporated
into
complex
natural
or
drugs
a
late
stage
site‐selectively,
which
has
not
been
shown
via
halides
aryldiazonium
salts.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5232 - 5277
Опубликована: Янв. 1, 2024
This
review
describes
recent
advances
in
the
generation
of
aryl
radicals
using
light
and
electricity.
Such
modern
techniques
allow
for
efficient
energy
resource
utilization,
thus
providing
more
sustainable
radical
arylation
methods.
Chinese Journal of Organic Chemistry,
Год журнала:
2022,
Номер
42(12), С. 4037 - 4037
Опубликована: Янв. 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 Chemistry Frontiers,
Год журнала:
2022,
Номер
10(4), С. 866 - 871
Опубликована: Дек. 21, 2022
Synthesis
of
β-azido
alkylsulfones
through
a
photoredox-catalyzed
azido
sulfonylation
alkenes
with
DABCO·(SO
2
)
,
trimethylsilyl
azide
and
alkyl
thianthrenium
salts
is
developed.
