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102 2 Transformation of Sulfoximines and Cyclic Sulfoximines
2.2.9 N–Sulfonyl Imine Formation
Sulfoximines can be changed into N–Sulfonyl imines by reacting with substances
that sulfonylate them. A sulfonyl imine motif is made when the sulfonyl group is
added to the nitrogen atom. This change makes the chemical diversity of sulfoximines
greater, opening up new ways to make synthetic compounds.
In conclusion, the pathways for changing sulfoximines give synthetic chemists a
lot of different tools they can use. These pathways allow the controlled modification
of sulfoximines, which gives us access to a wide range of functionalized derivatives.
Sulfoximines can be changed into thioethers, sulfoxides, amines, or other compounds
by reducing them, oxidizing them, or cleaving them. This makes them a useful
building block for making complex organic molecules that are used in many scientific
fields.
2.2.10 Cleavage of S=O and S=N Bonds
The cleavage of S=O (sulfoxide) and S=N (sulfinyl imine) bonds is a significant
and versatile transformation in organic chemistry that involves breaking the sulfur–
oxygen or sulfur–nitrogen bonds, respectively. These cleavage reactions are essential
in various synthetic processes, providing access to diverse molecular architectures
and facilitating the formation of new functional groups. Understanding the mecha-
nisms and conditions for these cleavage reactions is crucial for designing efficient
and selective synthetic pathways. This is the process of breaking the bond between
sulfur and oxygen in a sulfoxide functional group. It is also known as sulfoxide
cleavage. Sulfoxides have a sulfur atom with two oxygen atoms attached to it. They
react in unique ways that can be used in many synthetic processes.
There are different ways that the S=O bonds in sulfoxides can be broken,
depending on the reaction conditions and the type of substrate. One common way
is to reduce sulfoxides by treating them with reducing agents like metal hydrides
(like lithium aluminum hydride) or reducing agents based on boron. The sulfoxide
changes into a sulfide during the reduction process, which breaks the bond between
the sulfur and oxygen.
Misani and Reiner studied how to make methionine sulfoximine and how it reacts
with other chemicals in 1950. They were the first to describe a procedure resembling
how metabolism converts sulfoximines into sulfones (Scheme
2.48, Eq. a) [70
].
Bentley and Whitehead also looked into how the substance reacts with other things.
Sodium nitrite and hydrochloric acid were added to dimethylsulfoximine and cooked
to 75–80 °C. This made dimethyl sulfone (Scheme
2.48, Eq. b) [71]. Hachtel and
Gais wrote in 2000 that m-CPBA could be used to change sulfoximines into sulfones
(Scheme
2.48, Eq. c). Different N–Substituents, such as NH, N-alkyl, and N-benzyl
derivatives, could be used with this method [
72].
2.2 Conversion of Sulfoximines into Other Compounds 103
HO
S
O
H
2
N
H
O
NH
H
2
O
2
(30%)
acetic acid, 40
o
C, 6 d
HO
S
O
H
2
N
H
O
O
S
O
NH
NaNO
2
, HCl
H
2
O, 75-80
o
C
S
O
O
S
R
2
O
N
m-CPBA, HCl
THF, reflux
S
R
2
O
O
R
1
a)
b)
c)
Scheme 2.48 a Conversion of methionine sulfoximine to methionine sulfone with hydrogen
peroxide b conversion of dimethylsulfoximine to sulfone c conversion of sulfoximine to sulfone
with m-CPBA
Moreover, reductive cleavage of sulfoxides is a widely employed strategy, espe-
cially in the synthesis of complex molecules. The reducing agent donates electrons
to the sulfur atom, causing the reduction of the sulfur–oxygen bond. This process
often leads to the formation of a sulfur–carbon bond and the release of the oxygen
as a leaving group, resulting in the cleavage of the S=O bond. Sulfoxide cleavage
finds applications in various synthetic scenarios. In the synthesis of pharmaceuti-
cals, for instance, sulfoxides are commonly used as intermediates, and their subse-
quent cleavage allows for the introduction of diverse functionalities. Additionally,
sulfoxide cleavage can be employed in the deprotection of functional groups or in
the preparation of key building blocks for further synthetic manipulations.
The cleavage of S=O bonds in sulfoxides exhibits chemo- and regioselectivity,
allowing for precise control over the site of cleavage. The choice of reducing agent
and reaction conditions influences the selectivity, ensuring that the cleavage occurs
at the desired sulfur–oxygen bond without affecting other functionalities present in
the molecule.
Cleavage of S=N bonds (sulfinyl imine cleavage): This is the process of breaking
the bond between sulfur and nitrogen in sulfinyl imine functional groups. Sulfinyl
imines are chemicals that have a sulfur atom double-bonded to a nitrogen atom within
the imine moiety. Cutting them apart gives you access to different molecules that
contain amines. Mechanisms of sulfinyl imine cleavage: There are different ways to
achieve sulfinyl imine cleavage, and the method used depends on the needs of the
synthesis. A common method is to attack the nitrogen atom of the sulfinyl imine
with a nucleophile. Some nucleophiles, like amines or hydride sources, can react
with the sulfur–nitrogen bond. This can break the S=N bond and create a sulfide or
amine product. The nitrogen atom moves out of place during nucleophilic cleavage of
sulfinyl imines. This happens when a nucleophile attacks the sulfur atom. Different
nucleophiles, such as amines, hydride sources, or organometallic reagents, can speed
up this process. Depending on the nucleophile and the type of sulfinyl imine substrate,
the cleavage can happen in different areas. There are many ways that sulfinyl imine
104 2 Transformation of Sulfoximines and Cyclic Sulfoximines
cleavage can be used, but one of the most common is to make amines and other
similar compounds. Sulfinyl imines can be changed into amines through the cleavage
process. Amines are important building blocks in organic chemistry. This technique
is used to make complex molecules, such as pharmaceuticals and agrochemicals.
Just like sulfoxide cleavage, sulfinyl imine cleavage of S=N bonds shows chemo-
and regioselectivity. The reaction conditions and choice of nucleophile determine the
regioselectivity of the cleavage. This makes sure that only the desired sulfur–nitrogen
bond is cut, not any other parts of the molecule.
Sulfoxide cleavage and sulfinyl imine cleavage are two steps that are often used
together in multistep synthetic sequences. It is planned that these cleavage reactions
happen at key points in the synthesis process so that they can add certain functions.
Being able to selectively cut S=O or S=N bonds gives synthetic chemists powerful
tools for building complex molecular structures. The study of cleavage of S=O and
S=N bonds is always changing because new research is being done to find better,
more long-lasting, and more selective ways to do it. Researchers are looking for new
reagents, catalysts, and reaction conditions that can make these cleavage reactions
easier to control and more useful. Also, scientists are actively looking into how to
use cleavage strategies in cascade reactions and how to use these changes in a variety
of synthetic situations.
In ultimately breaking S=O and S=N bonds is an important and useful trans-
formation in organic synthesis. The sulfoxide cleavage and sulfinyl imine cleavage
reactions give chemists precise control over adding certain functions, which helps
them make different compounds. Because these cleavage reactions are s elective for
certain chemicals and regions, and because they can be used in multistep syntheses,
they are essential tools for synthetic chemists. As research goes on, these cleavage
strategies are likely to get better, which will make them more useful in synthetic
chemistry and help it move forward.
2.2.11 Conversion of Sulfoximines to Sulfoxides
Sulfoximines can be converted into sulfoxides, which is an important and useful
chemical change in organic chemistry. Sulfoximines can be selectively oxidized
to sulfoxides. They have a sulfur–nitrogen double bond within the imine func-
tional group. This oxidative change not only shows how flexible sulfoximines are as
synthetic building blocks, but it also gives us access to sulfoxides, which are flexible
chemicals that have many uses in medicine, materials science, and catalysis. For
those who are new to the process, converting sulfoximines to sulfoxides involves
selectively oxidizing the sulfur atom inside the sulfoximine moiety. This creates a
sulfoxide. This change is necessary to make the functional groups in a molecule more
diverse, and sulfoxides are useful in many synthetic processes because of how they
react differently.
Sulfoximines as precursors, because of how they react and are built, sulfoximines
are useful as precursors for this conversion. Sulfoximines have a sulfur–nitrogen
2.2 Conversion of Sulfoximines into Other Compounds 105
double bond that can be selectively oxidized. This lets sulfoxides be accessed in
a controlled way. Sulfoximines are very useful because they can be used in a lot
of different ways and are compatible with a wide range of oxidative conditions.
The conversion of sulfoximines to sulfoxides is typically achieved through oxida-
tive processes that involve the introduction of oxygen to the sulfur atom. Common
oxidants such as hydrogen peroxide, peracids, or metal-based oxidants can be
employed, depending on the desired reaction conditions and the substrate’s character-
istics. The choice of oxidant influences the efficiency, selectivity, and environmental
impact of the transformation.
The oxidation process turns sulfoximines into sulfoxides in a way that is selective
for certain chemicals and regions. This is one of the main benefits of this process.
The selective oxidation of the sulfur atom in the sulfoximine moiety makes sure that
it doesn’t interact too much with the molecule’s other functional groups. Regiose-
lectivity is controlled by where the sulfur atom is located in the sulfoximine. This
lets certain sulfoxide isomers be formed under controlled conditions.
It was shown by Oae and his colleagues that p-toluenesulfonyl nitrite, tert-
butyl nitrite, and tert-butyl nitrite can be used as organic nitrosyl cation sources
to turn sulfoximines into sulfoxides (Scheme
2.49, Eq. a) [73]. It is also possible
to change sulfoximines into sulfoxides by using pure sulfur and diphenyl disulfide
(Scheme
2.40, paragraph b). It was possible to make almost stoichiometric amounts
of diphenyl sulfoxide by heating diphenyl NH-sulfoximines and elemental sulfur to
160 °C for fifteen minutes (Scheme
2.49, Eq. b, method A) [74
]. You could also
make diphenyl sulfoxide by slowly heating a mixture of diphenyl sulfoximine and
diphenyl disulfide in 1,2-dichlorobenzene for five hours (Scheme
2.49, Eq. b, method
B) [
75].
After processing sulfoximines with phenyl(trihalomethyl)mercury as a dihalo-
carbene precursor at a temperature of 80 °C, Iqbal and Rahman discovered that a
combination of sulfoxides and oxosulfoniums was formed (Scheme
2.50)[76
].
For use in organic synthesis, making sulfoxides from sulfoximines can be used
in many different ways in organic synthesis. Because sulfoxides are found in many
natural products, pharmaceuticals, and agrochemicals, this change is very important
Scheme 2.49 a An organic
NO+ source is used to
convert sulfoximine to
sulfoxide b use elemental
sulfur or diphenyl disulfide
to convert sulfoximine to
sulfoxide
R
1
S
R
2
O
NH
p-TolSO
2
NO or t-BuSNO
2
MeCN, rt, 2-3 h
R
1
S
R
2
O
Ph
S
Ph
O
NH
method A: S
8
, 160
o
C, 15 min
method B: PhSSPh, reflux, 5 h
1,2-dichlorobenzene
Ph
S
Ph
O
a)
b)
Scheme 2.50 The
sulfoximines converted to
sulfoxides and
oxosulfoniums with the
dihalocarbene precursor
R
1
S
R
2
O
NH
PhHgCX
3
, benzene
80
o
C, 2-3 h
R
1
S
R
2
O
+
R
1
S
R
2
O
X
2
C
106 2 Transformation of Sulfoximines and Cyclic Sulfoximines
for making bioactive compounds efficiently. Besides that, sulfoxides have special
reactions that can be used in asymmetric synthesis, catalysis, and making molecular
probes. When sulfoximines undergo conversion into sulfoxides, molecular properties
change in ways that can affect how the new compounds behave. Sulfoxides and
sulfoximines often have different steric and electronic properties, which can change
things like how well they dissolve, react, and act biologically. This change in the
properties of molecules is important for making molecules that do certain things. In
certain cases, the conversion of sulfoximines to sulfoxides involves stereochemistry
considerations. If the sulfoximine precursor possesses stereocenters, the oxidation
process may result in the formation of chiral sulfoxides. This stereochemical control
is valuable in the synthesis of enantiomerically enriched sulfoxide products, which
have implications in asymmetric synthesis and medicinal chemistry.
Understanding the workings of the conversion process is important for making
sure that the reaction conditions are just right and that the oxidation of sulfoximines
to sulfoxides happens in a controlled way. Mechanistic studies help us understand
the intermediates that are made during oxidation, the oxidant’s role, and the factors
that affect selectivity. These new ideas help to improve the steps for reactions and
help us learn more about how sulfur changes in organic synthesis. The process of
changing sulfoximines to sulfoxides can happen with a number of different substrates,
which makes it possible to make a wide range of sulfur-containing compounds. But
the method might not work in all cases, depending on the functional groups in the
molecule and how well they work with the oxidants that were chosen. For substrates
that are hard to react with, the reaction conditions often need to be optimized. One
way to make sulfoxides is to change sulfoximines into sulfoxides. When you compare
this method to others, like oxidation of thioethers or reduction of sulfoxides, you can
see the pros and cons of each one. The method chosen is based on the specific needs
of the synthetic process and the sulfur-containing motif that is wanted.
The ongoing exploration of sulfoximine chemistry and its synthetic applica-
tions holds promise for future developments in the conversion to sulfoxides. Efforts
may focus on developing more sustainable and selective oxidation methodologies,
expanding the substrate scope, and exploring applications in areas such as medicinal
chemistry, materials science, and catalysis.
In conclusion, the conversion of sulfoximines to sulfoxides is a pivotal trans-
formation that exemplifies the adaptability of sulfoximines in organic synthesis.
This oxidative conversion not only provides access to sulfoxides, valuable building
blocks in diverse chemical contexts, but also showcases the controlled and selective
nature of the transformation. As part of the broader landscape of sulfur chemistry, the
conversion of sulfoximines to sulfoxides contributes to the rich repertoire of methods
available to synthetic chemists, offering efficiency, selectivity, and versatility in the
synthesis of complex organic molecules. The ongoing exploration of this conversion
and its integration into diverse synthetic sequences are poised to unveil new synthetic
possibilities and advance the field of sulfur-containing compound synthesis.
2.2 Conversion of Sulfoximines into Other Compounds 107
2.2.12 Conversion of Sulfoximines to Thioethers
The conversion of sulfoximines to thioethers is an example of a synthetic transforma-
tion that shows how useful sulfoximines are as building blocks in organic synthesis.
Sulfoximines have a sulfur–nitrogen double bond inside the imine functional group.
They can be changed selectively to thioethers using controlled reduction processes.
This change opens up a new way to get to compounds that contain thioether, which
increases the number of synthetic tools that can be used to make different molecular
structures.
When sulfoximines undergo a transformation to thioethers, the sulfur atom in
the sulfoximine moiety is reduced. This replaces the double bond between sulfur
and nitrogen with a single bond between sulfur and carbon. This chemical change
is important because it can change the functional groups inside a molecule while
keeping the structural support that the sulfoximine added. Sulfoximines as precursors,
because of how they react, sulfoximines are useful as precursors for this change.
The sulfoximine part, which has a sulfur atom directly connected to nitrogen, acts
as a handle for selective reduction. Sulfoximines are useful for making synthetic
chemicals because they can react with a wide range of conditions and can be changed
into different sulfur-containing compounds under controlled conditions.
Also, sulfoximines are usually changed to thioethers through reductive processes,
in which the sulfur atom is reduced to make a sulfide. This change can be sped
up by common reducing agents like hydride sources (like sodium borohydride or
lithium aluminum hydride) or transition metal catalysts. The chemoselectivity and
efficiency of the conversion depend on the reducing agent that is used. The ability
of the reduction process to choose which chemicals to use is one of the benefits of
changing sulfoximines to thioethers. In sulfoximines, the double bond between sulfur
and nitrogen is selectively reduced to a single bond between sulfur and carbon. This
doesn’t change any other functional groups in the molecule. This ability to selectively
select chemokines is especially useful in complicated synthetic schemes where other
functions must be kept.
Thioether-containing compounds exhibit unique molecular properties that can
influence their behavior in biological systems or materials applications. Thioethers
often enhance the lipophilicity of molecules, impacting their solubility and absorption
characteristics. This change in molecular properties can be leveraged in drug design
and the synthesis of functional materials.
The conversion of sulfoximines to thioethers finds applications across various
domains of organic synthesis. Thioethers are prevalent motifs in many natural prod-
ucts, pharmaceuticals, and agrochemicals, making this transformation crucial for the
efficient synthesis of bioactive compounds. Additionally, the introduction of thioether
linkages imparts distinct physicochemical properties to the molecules, influencing
factors such as lipophilicity and bioavailability.
In some cases, the conversion of sulfoximines to thioethers is intertwined with
reductive amination strategies. The reduction of sulfoximines to sulfides followed by
subsequent reductive amination allows for the introduction of amino functionalities,
108 2 Transformation of Sulfoximines and Cyclic Sulfoximines
Scheme 2.51 Conversion of
sulfoximines to thioethers
R
1
S
R
2
O
NH
KOH (50% aq.), CH
3
Cl
3
(NBnEt
3
)Cl (10 mol%)
DCM, rt, 2 h
R
1
S
R
2
further expanding the synthetic possibilities. This tandem approach showcases the
adaptability of sulfoximines in multistep synthetic sequences. Knowing how the
conversion process works is important for making sure that the reaction conditions
are just right and that the sulfoximines are reduced safely to thioethers. Mechanistic
studies help us understand the intermediates that are made during the reduction, the
reducing agent’s role, and the factors that affect selectivity. These new ideas help to
improve the steps for reactions and help us learn more about how sulfur changes in
organic synthesis.
The change from sulfoximines to thioethers can happen on a number of different
substrates, which makes it possible to make a wide range of sulfur-containing
compounds. The method may have some limits, though, depending on the functional
groups in the molecule and how well they work with the reducing agents that are
used. For substrates that are hard to r eact with, the reaction conditions often need to
be optimized. Changing sulfoximines to thioethers is only one way that sulfur can be
added to organic synthesis. When you compare one method to others, like thiolations
or sulfur ylide chemistry, you can see the pros and cons of each. The method chosen
is based on the specific needs of the synthetic process and the sulfur-containing motif
that is wanted.
It took a phase transfer agent, a solution that was half chloroform and half
potassium hydroxide, and some water for Oao and his colleagues to change the
sulfoximines into sulfides [
37
], as shown in Scheme
2.51.
The ongoing exploration of sulfoximine chemistry and its synthetic applications
holds promise for future developments in the conversion to thioethers. Efforts may
focus on developing more sustainable and selective methodologies, expanding the
substrate scope, and exploring applications in areas such as medicinal chemistry,
materials science, and catalysis.
In conclusion, converting sulfoximines into thioethers is a useful way to make new
compounds, showing how flexible sulfoximines are as building blocks for sulfur-
containing compounds. Controlled reduction processes make this change possible,
which gives a direct path to molecules containing thioethers and changes their phys-
ical and chemical properties as well as their uses. As part of sulfur chemistry, changing
sulfoximines to thioethers adds to the wide range of techniques that synthetic chemists
can use to make complex organic molecules. These techniques allow for flexibility
and selectiveness in the process. Researchers are still looking into this conversion and
how it can be used in different synthetic sequences. This could lead to new synthetic
possibilities and progress in the field of making sulfur-containing compounds.
References 109
2.2.13 Summary
Generally speaking, the transformation of sulfoximines occurs through reactions
involving a variety of chemical reagents. Methods that are commonly used include
oxidation to sulfoxides or reduction to sulfides. These methods enable structural
changes and the synthesis of a wide variety of compounds that have a variety of
characteristics. The particular transformation would be determined by the reaction
conditions that were selected as well as the final product that was wanted. One of
the most important aspects of organic synthesis is the transformation of sulfox-
imines, which provides an adaptable foundation for the development of a wide
variety of chemical compounds. Sulfoximines, which stand out due to a double
bond between sulfur and nitrogen, are capable of undergoing a variety of reactions
in order to synthesize useful compounds. Oxidation to sulfoxides and reduction to
sulfides are two examples of common transformations. Functional group modifica-
tions are another common chemical transformation. All of these techniques make it
possible to develop drugs, agrochemicals, and materials with characteristics that can
be adapted to specific needs. Because of their reactivity and selectivity, sulfoximine
transformations are an extremely useful tool in the field of modern organic chemistry.
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