Stereoselective addition of alpha-methylsulfenyl benzyl carbanions to N-sulfinylketimines: asymmetric synthesis of alpha,alpha-dibranched beta-sulfanyl amines.
(R)- and (S)-N-sulfinylketimines react with the ortho-sulfinyl benzyl carbanion derived from (S)-1 affording epimeric mixtures at the benzylic carbon of alpha,alpha-dibranched beta-sulfanyl amines. The N-sulfinyl group completely controls the configuration at the quaternary carbon bonded to the nitrogen, whereas the C-sulfinyl group is responsible for the level of asymmetric induction. High stereoselectivity can be achieved when the configuration at the sulfur atoms of the reagents are opposite (matched pair). After a two-step desulfinylation process, this reaction provides a procedure for synthesizing diastereomerically pure syn-1,2-sulfanyl amines containing a chiral quaternary carbon adjacent to nitrogen.
Arroyo
Yolanda
Y
Departamento de Quimica Organica (ETSII), Universidad de Valladolid, P del Cauce s/n, 47011 Valladolid, Spain.
Meana
Angela
A
Sanz-Tejedor
M Ascensión
MA
Alonso
Inés
I
García Ruano
José L
JL
D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D007097:Imines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D011789:Quantum Theory; D013237:Stereoisomerism; D013379:Substrate Specificity; D013434:Sulfenic Acids / Q000737:chemistry*
D000588:Amines; D007097:Imines; D013434:Sulfenic Acids