organosulfur chemistry Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulfur ...

, a thioketal is the

sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...

analogue of a

ketal In organic chemistry, an acetal is a functional group with the connectivity . Here, the R groups can be organic fragments (a carbon atom, with arbitrary other atoms attached to that) or hydrogen, while the R' groups must be organic fragments no ...

(), with one of the

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...

replaced by

(as implied by the ''

thio- The prefix thio-, when applied to a chemical, such as an ion, means that an oxygen atom in the compound has been replaced by a sulfur atom. This term is often used in organic chemistry. For example, from the word ''ether,'' referring to an ox ...

'' prefix), giving the structure . A dithioketal has ''both'' oxygens replaced by sulfur (). Thioketals can be obtained by reacting

ketones In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bon ...

() or

aldehydes In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl grou ...

() with

thiols In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl grou ...

(). An oxidative cleavage mechanism has been proposed for dithioketals, which involves thioether oxidation, the formation of thionoiums, and

hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...

, resulting in the formation of aldehyde and ketone products. Thioketal moieties are found to be responsive to

reactive oxygen species In chemistry, reactive oxygen species (ROS) are highly reactive chemicals formed from diatomic oxygen (). Examples of ROS include peroxides, superoxide, hydroxyl radical, singlet oxygen, and alpha-oxygen. The reduction of molecular oxygen () p ...

(ROS). In the presence of ROS, thioketals can be selectively cleaved. ROS successfully cleave heterobifunctional thioketal linkers, which have been found to have therapeutic potential, as they can produce ROS-responsive agents with two different functionalities. Ketones can be reduced at neutral pH via conversion to thioketals; the thioketal prepared from the ketone can be easily reduced by catalytic hydrogenation using Raney nickel in a reaction known as the

Mozingo reduction The Mozingo reduction, also known as Mozingo reaction or thioketal reduction, is a chemical reaction capable of fully reducing a ketone or aldehyde to the corresponding alkane via a dithioacetal. The reaction scheme is as follows: The ketone o ...

References

{{orgchem-stub Functional groups Organosulfur compounds

See also

References