Sulfinamides do not undergo inversion. They can therefore be synthesised and/or isolated in enantiopure forms. This has led to their use as chiral
ammonia equivalents and more broadly as
chiral auxiliaries.
Synthesis
Sulfinamides are traditionally produced by the reaction of
sulfinyl chlorides with primary or secondary amines.[1] They also arise by the addition of
Grignard reagents to
sulfinylamines, followed by protonation:
RMgX + R'N=S=O → RS(O)(NR'MgX)
RS(O)(NR'MgX) + H2O → RS(O)(NR'H) + "MgX(OH)"
Yet another route entails peracid-oxidation of sulfenylphthalimides, which gives sulfinylphthalimides.
Sulfinamides arise in nature by the addition of
nitroxyl (HNO) to
thiols:[6]
RSH + HNO → RS(O)NH2
References
^
abJ. G. Tillett (1981). "Sulphinamides". In Saul Patai (ed.). Sulphinic Acids, Esters and Derivatives. PATAI'S Chemistry of Functional Groups. John Wiley & Sons. pp. 185–215.
doi:
10.1002/9780470772270.ch7.
ISBN978-0-471-91918-6.
^Eccles, K. S.; Morrison, R. E.; Daly, C. A.; O'Mahony, G. E.; Maguire, A. R.; Lawrence, S. E. (2013). "Co-crystallisation Through Halogen Bonding with Racemic or Enantiopure Sulfinamides". CrystEngComm. 15 (37): 7571–7575.
doi:
10.1039/C3CE40932E.