Sulfilimine Explained

In chemistry, a sulfilimine (or sulfimide) is a type of chemical compound containing a sulfur-to-nitrogen bond which is often represented as a double bond . In fact, a double bond violates the octet rule, and the bond may be considered a single bond with a formal charge of +1 on the sulfur and a formal charge of −1 on the nitrogen. The parent compound is sulfilimine, which is mainly of theoretical interest.

Examples include S,S-diphenylsulfilimine[1] and sulfoximines  such as methylphenylsulfoximine:[2] In the case of a sulfoximine, the bonds can be considered single bonds, with formal charges of −1 on both the oxygen and the nitrogen, and a formal charge of +2 on the sulfur.

Preparation

Most sulfilimines are N-substituted with electron-withdrawing groups. These compounds are typically prepared by oxidation of thioethers with electrophilic amine reagents, such as chloramine-T in the presence of a base:[3]

An alternative route involves reactions of electrophilic sulfur compounds with amines. The imidosulfonium reagents provide a source of "", which are attacked by amines.

Sulfilimine bonds in proteins

Sulfilimine bonds stabilize collagen IV strands found in the extracellular matrix[4] and arose at least 500 mya.[5] These bonds covalently connect hydroxylysine and methionine residues of adjacent polypeptide strands to form a larger collagen trimer.

Notes and References

  1. Web site: S,S-Diphenylsulfilimine . Sigma-Aldrich .
  2. Web site: (R)-(−)-S-Methyl-S-phenylsulfoximine . Sigma-Aldrich .
  3. 10.1021/cr60307a005. The chemistry of sulfilimines. 1977. Gilchrist. Thomas L.. Moody. Christopher J.. Chemical Reviews. 77. 3. 409–435.
  4. Science . A sulfilimine bond identified in collagen IV. . 325 . 5945 . 1230–1234 . September 4, 2009 . Vanacore R, Ham AL, Voehler M, Sanders CR, Conrads TP, Veenstra TD, Sharpless KB, Dawson PE, Hudson BG . 19729652. 2876822 . 10.1126/science.1176811. 2009Sci...325.1230V.
  5. 10.1073/pnas.1318499111 . A unique covalent bond in basement membrane is a primordial innovation for tissue evolution . 2014 . Fidler . Aaron L. . Vanacore . Roberto M. . Chetyrkin . Sergei V. . Pedchenko . Vadim K. . Bhave . Gautam . Yin . Viravuth P. . Stothers . Cody L. . Rose . Kristie Lindsey . McDonald . W. Hayes . Clark . Travis A. . Borza . Dorin-Bogdan . Steele . Robert E. . Ivy . Michael T. . Hudson . Julie K. . Hudson . Billy G. . Hudson . Billy G. . Proceedings of the National Academy of Sciences . 111 . 1 . 331–336 . free . 24344311 . 3890831 . 2014PNAS..111..331F .