S(N)1-like reactions of bicyclic alpha-amino ethers with sulfur, nitrogen, and carbon nucleophiles. Synthesis of 1-azabicyclo[3.2.2]nonanes functionalized at carbon C2 and C6 with complete stereocontrol.
[reaction: see text] In the presence of nucleophiles, Lewis acid mediated cleavage of alpha-amino ethers derived from quincorine and quincoridine affords a variety of C2-substituted and C6-vinylated 1-azabicyclo[3.2.2]nonanes. These are enantiopure and are formed in S(N)1-like reactions with complete stereocontrol. There is no leakage into 2-Nu en route to product 1-Nu or vice versa. Me(3)SiCN provides new Strecker-type alpha-amino nitriles. In the presence of TTMPP-BF(3).OEt(2), the ketene acetal Me(2)C=C(OMe)OSiMe(3) delivers enantiopure bicyclic beta-amino acid esters.
Röper
Stefanie
S
Department of Organic Chemistry, University of Hannover, Schneiderberg 1B, Germany.
Wartchow
Rudolf
R
Hoffmann
H Martin R
HM
D001372:Aza Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*
D001372:Aza Compounds; D004987:Ethers; D013455:Sulfur; D002244:Carbon; D009584:Nitrogen