Asymmetric synthesis of indolines through intramolecular shifting of aromatic sulfinyl groups. Role of the pi,pi-stacking interactions in these unusual S(N)Ar processes.
Cyclization of N-aryl substituted 1-aryl-2[2-p-tolylsulfinyl]phenyl propylamines under LDA, LHMDS, or KHMDS provides a new approach for synthesizing optically pure 2,3-disubstituted indolines. Both the scope and the limitations of this method have been investigated. The pi,pi-stacking interactions are crucial for these unprecedented intramolecular S(N)Ar processes, in which a sulfinyl group located on a slightly deactivated ring is substituted by amide anions under mild conditions. X-ray and NMR proofs supporting these pi,pi-stacking interactions are presented.
García Ruano
José L
JL
Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. joseluis.garcia.ruano@uam.es
Parra
Alejandro
A
Marcos
Vanesa
V
del Pozo
Carlos
C
Catalán
Silvia
S
Monteagudo
Silvia
S
Fustero
Santos
S
Poveda
Ana
A
D018360:Crystallography, X-Ray; D003500:Cyclization; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D011437:Propylamines / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*
D007211:Indoles; D011437:Propylamines; C057812:indoline; D013455:Sulfur