Synthesis of secondary amines by titanium-mediated transfer of alkenyl groups from alcohols.
Reaction of Ti(NMe2)4 with allyl alcohols and primary amines leads to the selective formation of secondary allylic amines. The allyl transfer from the alcohol to the amine occurs with selective allylic transposition. Due to substituent effects in the reactions, we postulate that the reaction occurs through a [2 + 2]/retro-[2 + 2]-cycloaddition mechanism. It was also found that a similar reaction could be accomplished with homoallylic alcohol. In this case, the more complex mechanism leads to the formation of 1-aza-spiro[5.5]undecane. Possible pathways for the homoallylic transfer and cyclization are discussed.
Ramanathan
Balasubramanian
B
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA.
Odom
Aaron L
AL
D000438:Alcohols / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis*; D002384:Catalysis; D015394:Molecular Structure; D014025:Titanium / Q000737:chemistry*
D000438:Alcohols; D000588:Amines; D014025:Titanium