Asymmetric lithiation-substitution sequences of substituted allylamines.
[reaction: see text] (-)-Sparteine-mediated asymmetric lithiation-substitution sequences of 2- and 3-substituted N-(Boc)-N-(p-methoxyphenyl) allylic amines with electrophiles have been investigated. Asymmetric lithiation-substitutions of N-(Boc)-N-(p-methoxyphenyl) allylic amines 11, 12, 13, 14, and 15 provide highly enantioenriched enecarbamates in good yields. Further transformations to give aldehydes, acids, ketones, and a Diels-Alder adduct are reported. The 1,4-addition products from reactions of the lithiated allylic amines from 14 and 15 with conjugated activated alkenes gives enecarbamates with two and three stereogenic centers in good yields with high diastereomeric and enantiomeric ratios. Synthetic transformation of these products by acid hydrolysis and subsequent cyclization provide stereoselective access to bicyclic compounds containing four and five stereogenic centers with high diastereoselectivity and enantioselectivity. It is suggested that allyllithium complexes generated by asymmetric deprotonation react with most electrophiles with inversion of configuration.
Kim
Dwight D
DD
Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
Lee
Suk Joong
SJ
Beak
Peter
P
D000475:Alkenes / Q000737:chemistry; D000499:Allylamine / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D003500:Cyclization; D008094:Lithium / Q000737:chemistry*; D015394:Molecular Structure; D011522:Protons; D013237:Stereoisomerism
D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D011522:Protons; D000499:Allylamine; D008094:Lithium