N-Acyliminium Ion Rearrangements

BnO BnO O
OAc OAc OBn
O OH
NaBH4, H OH N
Me OAc
Me N MeOH, Me N
Me O
Me O Me O

[3,3]

O BnO OAc
BnO OAc H OBn
H Me
Me H O N OAc
Me
HCO2 N
N Me
Me Me O H
O
O

HO OH
H
Synthesis of (-)-hastanecine: Hart JOC 1985, 50, 235.
(-)-hastancine
N
 Aza-Cope Manich Reactions
OR OR
OR OR

CH2O, Na2SO4 N N [3,3] N

N
H MeCN, 80ÞC HO
HO HO
HO
NR2 NR2 NR2
NR2

OR

ROH2C
N
N Mannich N
Rxn
HO
O O
OR
NR2
NR2
NR2 Axial Attack

H
N Overman et al. JACS 1995, 117, 5776.
H
O
HO
strychnine