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42 1 Synthesis of Sulfoximines and Cyclic Sulfoximines
palladium-catalyzed coupling of terminal alkynes with aryl or vinyl halides at the
terminal position. Alkynes can be introduced into cyclic sulfoximines by the use of
this approach, which enables the formation of more complicated compounds. The
aza-Huisgen cycloaddition reaction is a type of reaction in which azides react with
alkynes to generate triazoles. Alkynes are able t o take part in this reaction. A wide
variety of cyclic structures can be obtained through the utilization of this method,
which enables the insertion of sulfoximines into the triazole ring.
The modification of cyclic sulfoximines can be customized and controlled by the
use of these reactions, which give synthetic flexibility. When it comes to achieving the
desired regio- and stereoselectivity, the choice of reaction conditions and catalysts is
more important than ever. Medicinal chemistry, materials science, and other sectors
where the development of one-of-a-kind cyclic structures is essential are some of the
potential uses for the molecules that were produced as a result. When it comes to
the synthesis of cyclic sulfoximines, the adaptability of alkynes as coupling partners
stands out as a significant advantage.
From a broader point of view, it was commonly believed that terminal alkynes
were not compatible with the Rh(III) catalytic system due to the presence of active
hydrogen atoms. An innovative approach to the synthesis of 1,2-benzothiazines was
described by Prabhu and colleagues in 2019. This method involved the use of diphenyl
sulfoximines 72 and alkynyl silanes 73 as substrates, which were then catalyzed by
the Rh(III) catalytic system (Scheme
1.47)[78
]. Without much difficulty, the TMS
group was extracted from the alkynyl silanes in the presence of AgSbF
6
and water,
which resulted in the formation of the required motifs. For this reaction to take place,
oxygen was required. Low to moderate yields (32–67%) were achieved for a series
of 1,2-benzothiazine derivatives that contained a free substituent at the C-4 position.
These derivatives had the ability to change into different functional scaffolds. There
is also the possibility that the relatively low yields are due to the breakdown of the
sulfoximines.
Scheme 1.48 provides a demonstration of the possible mechanism. At the begin-
ning of the cycle, AgSbF
6
and Cu(OAc)
2
·H
2
O are essential components that play
a crucial role in the activation of the catalyst. Following this, K1 forms the five-
membered rhodacycle complexes K2 by coordinating with sulfoximines 72. The
intermediates K3 are then produced as a result of the insertion of arylalkynyl
S
O
NH
R
R
+
TMS
R
1
[RhCp*Cl
2
]
2
(5 mol%)
AgSbF
6
(20 mol%)
Cu(OAc)
2
·H
2
O, H
2
O
O
2
, PhMe, 100
o
C, 4 h
S
O
R
R
N
R'
(32–67%)
72
73
74
Scheme 1.47 The synthesis of 1, 2-benzothiazines in the Rh(III) catalytic system using alkynyl
silanes
1.2 Synthesis of Cyclic Sulfoximines 43
silanes 73. In the end, the products 74 are acquired through the process of reductive
elimination of K3, and the active catalyst K1 is also regenerated.
In the same year, Prabhu developed a Rh(1/6)-catalyzed cascade C−H activation,
regioselective annulation, and lactonization method for the synthesis of furanone-
fused 1,2-benzothiazines derivatives 77a. This strategy involved the use of sulfox-
imines 75 and 4-hydroxy-2-alkynoates 76, as illustrated in Scheme
1.49 [79]. In
addition to demonstrating regioselectivity in the formation of single regioisomers
77a in moderate to good yields, the reaction showed a high level of functional group
tolerance. It is possible that the steric interaction between the hydroxyl oxygen atom
and the Rh(III) center is the reason why the other regioisomer 77b was not discovered.
In the year 2020, Li et al. demonstrated the Pd(II)-catalyzed C–H functional-
ization/cyclization of sulfoximines 78 with aryne precursors 79 in order to generate
tricyclic dibenzothiazines 80. This was accomplished by employing Pd(OAc)
2
as the
most effective catalyst and CuO as the oxidant (Scheme
1.50)[80]. The performance
of a number of sulfoximines that contained electron-rich, halogen, and S-substituents
[RhCp*Cl
2
]
2
[Cp*Rh(OAc)][SbF
6
]
AgSbF
6
2AgCl
Cu(OAc)
2
·H
2
O
Rh
N
S
O
Ar
Cp*
S
O
NH
Ar
AcOH
TMS
Rh
N
S
O Ar
TMS
Cp*
Cu(OAc)
2
·H
2
O + O
2
S
O
N
K1
K2
K3
72
73
74
R
R
R
R
R
R
1
R
1
R
1
Scheme 1.48 Proposed mechanism of annulation of sulfoximines and alkynyl silanes in the Rh
catalytic system
44 1 Synthesis of Sulfoximines and Cyclic Sulfoximines
S
O
HN
R
2
R
1
+
OTf
TMS
R
3
Pd(OAc)
2
(10 mol%)
CuO, CsOAc, CsF
1-Ad-CO
2
H, Dioxane, 110
o
C, 24 h
N
S
O
R
2
R
1
R
3
27 examples (50-80%)
78
79
80
Scheme 1.49 Tandem Rh(III)-catalyzed C–H activation of sulfoximines to furnish furanone-fused
1,2-benzothiazines derivatives
S
O
HN
R
2
R
1
+
OTf
TMS
R
3
Pd(OAc)
2
(10 mol%)
CuO, CsOAc, CsF
1-Ad-CO
2
H, Dioxane, 110
o
C, 24 h
N
S
O
R
2
R
1
R
3
27 examples (50-80%)
78
79
80
Scheme 1.50 Pd(II)-catalyzed C–H functionalization strategy for the preparation of dibenzoth-
iazines
was satisfactory, and the naphthyl-sulfoximine produced a mixture of regioselective
products.
The depicted mechanism is presented in Scheme 1.51. At first, Pd(OAc)
2
directly
interacts with sulfoximines 78 to produce the acyclic Pd species L2, while simulta-
neously releasing AcOH. Subsequently, the in-tramolecular deprotonation process
results in the formation of five-membered palladium cyclic complexes L3, accompa-
nied by the elimination of an additional molecule of AcOH. Following that, benzyne
insertion takes place, resulting in the formation of seven-membered cyclic palla-
dium complexes L4. Finally, L4 undergoes a reductive elimination route to produce
the compounds 80. At the same time, the catalyst L1 is restored via the process of
reoxidation, where Pd(0) is converted back to Pd(II) in the presence of the copper
salt.
To sum up, the reactions described in this chapter provide a means of altering
and regulating the structure of cyclic sulfoximines with a high degree of flexibility.
Optimal selection of reaction conditions and catalysts is crucial in order to attain
the intended regio- and stereoselectivity. The resultant molecules have potential uses
in medical chemistry, materials science, and other domains where the generation of
distinct cyclic structures is crucial. The ability of alkynes to be used as coupling
partners emphasizes their usefulness in the synthesis of cyclic sulfoximines by C–H
bond activation.
1.2 Synthesis of Cyclic Sulfoximines 45
Pd(OAc)
2
S
O
NH
R
2
AcOH
S
O
N
R
2
PdOAc
AcOH
Pd
N
S
O
R
2
TfO
TMS
F
Pd
N
S
O
R
2
CuO
N
S
O
R
2
L2
L3
L4
80
78
79
L1
R
1
R
1
R
1
R
1
R
1
R
3
R
3
R
3
R
3
Scheme 1.51 Proposed mechanism of Pd-catalyzed annulation of sulfoximines with arynes
1.2.7 Synthesis of Cyclic Sulfoximines via Intramolecular
C–H Activation
The synthesis of cyclic sulfoximines via intermolecular C–H activation involves the
direct functionalization of carbon-hydrogen (C-H) bonds within a molecule to form
a sulfoximine ring. To make this process easier, transition metal catalysts are often
used. For making cyclic sulfoximines using intermolecular C–H activation, here is a
general method; choice of substrate, choose a good starting material that has a C–H
bond that needs to be triggered. The selectivity and effectiveness of the C–H activation
will depend on the substrate that is used. Transition metal catalyst, select the right
transition metal catalyst that can set off C–H bonds. Rhodium, ruthenium, or iridium
combinations are often used catalysts. The material and the reaction conditions that
are wanted determine which catalyst is best. Adding a sulfoximine precursor to
the reaction mixture is the next step. Usually, this precursor has a good end group
that can be switched out during the C–H activation process. Reaction conditions;
find the best favorable temperature, solvent, and reaction time for the reaction so
that the C–H group can react and make sulfoximine. Based on the material and
catalyst that are used, the conditions may be different. Activation of the C–H bond
and formation of sulfoximine: The transition metal catalyst triggers the C–H bond
in the substrate, creating a reactive intermediate. The sulfoximine precursor goes
through substitution at the active C–H site at the same time, which makes the cyclic
46 1 Synthesis of Sulfoximines and Cyclic Sulfoximines
sulfoximine product. Workup and Purification: When the reaction is done, stop it
or cool it as needed. Clean up the chemical mixture to get the cyclic sulfoximine
product you want. Chromatography and recrystallization are two common ways to
clean something. Characterization: Use analytical methods like NMR spectroscopy,
mass spectrometry, and, if needed, X-ray crystallography to confirm the structure of
the separated product to characterize it.
By activating C–H bonds, this method makes it possible to add a sulfoximine
moiety directly to a circular structure. The conditions and catalyst can be changed
depending on the substrate and the level of selectivity that is needed for the C–H
activation. As with any synthetic method, the reaction and substrate used can indicate
that the conditions of the experiment need to be changed to get the best results.
In 2018, Zhang et al. published a study describing a way to synthesize
benzothiazines 82 without the use of metals. This method involves a one-pot
process that combines N,O-transfer and intramolecular C–H amination of 2-
biphenylsulfoximines 81. The process is illustrated in Scheme
1.52 and was
detailed in reference [
81]. The outcome of the investigation on reaction circum-
stances revealed that the utilization of (NH
4
)
3
PO
4
·3H
2
O as the nitrogen source and
PhI(OAc)
2
as the oxidizing agent was imperative in order to produce the products
82 with significant yields. The hypothesized mechanism investigations indicate that
PhI(OAc)
2
can act as a free radical initiator for NH-sulfoximines, leading to the
formation of the important intermediates 84 and 85 in a feasible pathway. In addi-
tion, this technique can be applied to a wide range of substrates. Different compounds
of dibenzothiazine can be easily obtained, with yields ranging from 24 to 94%.
S
R
3
R
1
R
2
(NH
4
)
3
PO
4
·3H
2
O, PhI(OAc)
2
DMF, rt
S
R
3
R
1
R
2
N
O
S
R
3
R
1
R
2
O
NH
S
R
3
R
1
R
2
O
N
I
Ph
OAc
S
R
3
R
1
R
2
O
N
84
85
24 examples(24–94%)
81
82
83
Scheme 1.52 Metal-free method for the intramolecular C–N coupling to form benzothiazines
1.2 Synthesis of Cyclic Sulfoximines 47
S
R
3
R
1
R
2
1) (NH
4
)
6
Mo
7
O
24
·4H
2
O,
PhI(OAc)
2
, DMF, rt, 1 h
2) I
2
, 80
o
C, 12 h
S
R
3
R
1
R
2
O
N
II
or
S
R
3
R
1
R
2
O
N
I
18 examples (13–85%)
86
87
88
Scheme 1.53 Tandem C–H activation and C–N coupling of sulfoximines to form iodo-thiazines
Zhang’s group conducted more research on the one-pot N,O-transfer and
intramolecular C–H amination of 2-biaryl sulfides 86. This resulted in the synthesis of
a range of iodo-dibenzothiazines compounds 87, as shown in Scheme
1.53 [82]. Addi-
tionally, monoiodo-dibenzothiazines 88 were detected in cases where the 4
-positions
of sulfides were replaced by bulky steric hindrance substituents or strong electron-
withdrawing substituents like CF
3
. In addition, the required products can be converted
into various functional thiazine compounds by the process of cross-coupling reaction.
In 2019, Ma and his colleagues published a metal-free tandem amina-
tion/bromination approach for the synthesis of bromobenzothiazines 90. This
method was achieved through the intramolecular C–H activation of N-methyl-2-
biphenylsulfonamides and 2-biphenylsulfoximines 89, as shown in Scheme
1.54
[83]. It is interesting to note that, in contrast to the substrates of sulfonamides, sulfox-
imines were able to produce di-bromothiazines as the sole products, while momo-
bromothiazines were not discovered under the circumstances that are considered
typical.
One year later, Zhang and Chen developed a step-economic dibromohydantoin
(DBH)-promoted cyclization strategy for the synthesis of bromo-N-heterocycles 93
from the 2-biphenyl sulfoximines 91 in water (Scheme
1.55)[84]. Moreover, this
novel strategy fulfilled the synthesis of various N-heterocycles products in moderate
to good yields and up to > 20:1 dr, and the substrate scope was also extended to
2-biphenyl phosphamides.
In conclusion, sulfoximine ring is formed by directly functionalizing carbon-
hydrogen (C-H) bonds within a molecule in the process of synthesizing cyclic sulfox-
imines through intermolecular C–H activation. Catalysts made of transition metals
are commonly used to make this process easier. This method activates C–H bonds,
allowing a sulfoximine moiety to be directly incorporated into a cyclic structure. The
Scheme 1.54 Metal-free
tandem amination/
bromination protocol for the
synthesis of
bromobenzothiazines
S
R
3
O
NH
R
1
R
2
K
2
S
2
O
8
, NaBr
H
2
O, 80
o
C
S
R
3
O
N
R
1
R
2
Br Br
8 examples (31-89%)
89
90
48 1 Synthesis of Sulfoximines and Cyclic Sulfoximines
S
O
NH
R
1
R
+
N
N
O
O
Br
Br
H
2
O, 100
o
C
S
O
N
R
1
R
Br Br
4 examples
(46-86%, dr>20:1)
91 92 93
Scheme 1.55 The cyclization of sulfoximines by DBH-promoted tandem C–H amination/
bromination
substrate and the required regioselectivity of the C–H activation can be taken into
account when determining the exact conditions and catalyst to be utilized. Depending
on the reaction and substrate used, experimental parameters may need to be adjusted,
as is the case with any synthetic method.
1.2.8 Miscellaneous
In the field of cyclic sulfoximines, the term miscellaneous reactions refer to a variety
of synthetic transformations or processes that might not be able to be neatly classified
into specific categories, but are remarkable for their variety and utility. The adapt-
ability of cyclic sulfoximines as synthetic intermediates is demonstrated by these
various reactions, which also illustrate the inventiveness that is required to create
novel transformations. Researchers frequently investigate and improve these varied
reactions in order to gain access to new compounds and to broaden the application
of cyclic sulfoximines in a variety of scientific and industrial contexts.
Pd/norbornene-catalyzed coupling reaction for the synthesis of fused poly-
cyclic sulfoximines 96 with 2-bromo-NH-sulfoximines 94 and aryl iodides 95
was described by Chen and colleagues in 2018, as shown in Scheme
1.56 [85
].
This reaction was catalyzed by Pd/norbornene system. While it was established
that PPh
3
is the most effective ligand, it was also demonstrated that norbornene
is required for this reaction. In addition, the spectrum of substrates was investi-
gated under optimized conditions. It was determined that the reaction between aryl
iodides and ortho-bromophenyl sulfoximines was successful in producing the neces-
sary products in satisfactory quantities. Furthermore, aryl iodides that contained
electron-withdrawing groups, such as CO
2
Me and CF
3
, also underwent a natural
transformation. On the other hand, the reaction process would be impacted by the
ortho-substituent.
This evaluation can motivate a greater number of researchers to come up with
more remarkable ideas and to discover more important new experimental proce-
dures. Cyclic sulfoximines can be used in the following processes, some of which
have described and some of which have not: Reduction reactions can change the
1.2 Synthesis of Cyclic Sulfoximines 49
S
Br
O
NH
R
2
R
1
+
I
R
3
R
4
Pd(OAc)
2
, PPh
3
, norbornene
K
2
CO
3
, MeCN, 85-105
o
C, 12 h
R
1
N
S
O
R
2
R
3
R
4
21 examples (45
95%)
94
95
96
Scheme 1.56 Pd/norbornene-catalyzed coupling reaction for the synthesis of fused polycyclic
sulfoximines
sulfoximine functional group into a sulfide or an amine. These reactions can also
be used on cyclic sulfoximines with reduction processes. It’s possible that reducing
agents like hydrides or metal catalysts will be used in this. Changing cyclic sulfox-
imines through oxidative processes: These processes can either add new functional
groups or change the ones that are already there. It’s possible that this will use
metal-based oxidizing agents or oxidants like peroxides. Halogenation events can
add halogen atoms like fluorine, chlorine, bromine, or iodine. Maybe this will either
make cyclic sulfoximines more reactive or change the way they work physically
and chemically. Desulfurization: In desulfurization processes, sulfur atoms are taken
away from the sulfoximine moiety. This creates amines that are similar to the elements
that contain sulfur atoms. It is possible to make this change with a number of different
lowering agents. Reactions that cross-couple: It is possible to connect cyclic sulfox-
imines with other chemicals through cross-coupling reactions, which gives them new
roles. Within the scope of this talk, cross-coupling processes facilitated by palladium
are very common. One-pot reactions happen in a single pot and are called cascade
reactions because three or more reactions happen one after the other. It’s possible
that these reactions will quickly and effectively make complicated compounds that
contain cyclic sulfoximines. Reactions that use light to start chemical reactions:
photochemical reactions can change many different kinds of cyclic sulfoximines
into other chemicals. Because of these responses, new routes can be made that might
not be possible in normal conditions. Bioconjugation processes: Bioconjugates can
be made from cyclic sulfoximines through processes that work with living things. It
is possible that this could be used in medicinal science and other areas.
1.2.9 Summary
In this study, a number of methods that have been described in the past several
years for the synthesis of cyclic sulfoximines through the activation of C–H
bonds have been taken into consideration and summarized. Various coupling part-
ners including diazo compounds, sulfoxonium ylides, iodonium ylides, benzyl
azides, N-alkoxyamides, 1,4,2-dioxazol-5-ones,α,β-unsaturated ketones, alkynyl
silanes, 4-hydroxy-2-alkynoates, and arynes were successfully assembled with NH-
sulfoximines, forming the corresponding [4 + 2] or [4 + 3] annulation products
50 1 Synthesis of Sulfoximines and Cyclic Sulfoximines
bearing a variety of substituents. Despite the significant progress that has been
made in this field, there are still a number of limits that exist. The catalysts that
are regularly used, such as Ru(II) and Rh(III), are expensive, whereas the catalysts
that are quite inexpensive, such as Co(III), have not been utilized extensively or
have performed extremely poorly. Despite the fact that metal-free methods are still
restricted to intramolecular reactions, the range of substrates that can be used is often
limited. With the exception of the nitrogen atom, it has not been documented that any
other heteroatoms are incorporated into the cyclic sulfoximines of the compound. In
addition, the cyclic compounds that are produced are closely related to sulfoximines
that have six or seven members.
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