Organolanthanide-catalyzed intramolecular hydroamination/cyclization of amines tethered to 1,2-disubstituted alkenes.
[reaction: see text] This contribution reports the organolanthanide-catalyzed intramolecular hydroamination/cyclization of amines tethered to 1,2-disubstituted alkenes to afford the corresponding mono- and disubstituted pyrrolidines and piperidines by using coordinatively unsaturated complexes of the type (eta(5)-Me(5)C(5))(2)LnCH(TMS)(2) (Ln = La, Sm), [Me(2)Si(eta(5)-Me(4)C(5))(2)]NdCH(TMS)(2), [Et(2)Si(eta(5)-Me(4)C(5))(eta(5)-C(5)H(4))]NdCH(TMS)(2), and [Me(2)Si(eta(5)-Me(4)C(5))((t)()BuN)]LnE(TMS)(2) (Ln = Sm, Y, Yb, Lu; E = N, CH) as precatalysts. [Me(2)Si(eta(5)-Me(4)C(5))((t)BuN)]LnE(TMS)(2) mediates intramolecular hydroamination/cyclization of sterically demanding amino-olefins to afford disubstituted pyrrolidines in high diastereoselectivity (trans/cis = 16/1) and in good to excellent yield.
Ryu
J S
JS
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
Marks
T J
TJ
McDonald
F E
FE
D000475:Alkenes / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry; D010880:Piperidines / Q000138:chemical synthesis*; D011759:Pyrrolidines / Q000138:chemical synthesis*
D000475:Alkenes; D000588:Amines; D028581:Lanthanoid Series Elements; D009942:Organometallic Compounds; D010880:Piperidines; D011759:Pyrrolidines