SYNTHESIS WITH ORGANOBORANES. I. SYNTHESIS OF ALLYLIC DIETHYLBORANES AND B-ALLYLIC BORINANES VIA METALATION OF OLEFINS. CONTRATHERMODYNAMIC ISOMERIZATION OF OLEFINS

Article abstract of DOI:10.1016/0022-328X(85)80282-5

Allylic organopotassium compounds prepared by metalation of olefins with trimethylsilylmethylpotassium reacted with chlorodiethylborane and b-chloroborinane to give allylic diethylboranes and B-allylic borinanes, respectively.Hydrolysis of these organoboranes proceeding with allylic rearrangement leads to isomerized olefins.In this way, (E,Z)-2-pentene, (Z)-2-heptene, 1-methylcyclohexene and (+)-α-pinene were cleanly transformed into 1-pentene, 1-heptene, methylenecyclohexane and (+)-β-pinene, respectively.Stereochemistry of the addition of myrtenyldiethylborane toformaldehyde and 2-cyclohexenyldiethylborane to 4-t-butylcyclohexanone is described.