4-Hydroxylated Piperidines and N-Methyleuphococcinine (1-Methyl-3-granatanone) from Picea (Spruce) Species. Identification and Synthesis

Abstract
Three trace alkaloids from Colorado blue spruce, Picea pungens, were identified by synthesis and GC−MS comparisons as 4α-hydroxy-cis-2-methyl-6-(2-oxopropyl)piperidine (1), 4α-hydroxy-cis-2-methyl-6-propylpiperidine (11), and 1-methylgranatanone (15) (N-methyl-9-aza-1-methylbicyclo[3.3.1]nonane or N-methyleuphococcinine). Alkaloids 1 and 11 are the first among numerous known pine and spruce piperidines to contain a ring-oxygenated substituent.