Chiral Synthesis via Organoboranes. 47. Efficient Synthesis of
Unsymmetrical Ketones and Enantiomerically Pure Spiroketals
Using (±)-Isopinocampheyldichloroborane
posted on 1998-09-15, 00:00authored byHerbert C. Brown, Shekhar V. Kulkarni, Uday S. Racherla, Ulhas P. Dhokte
Readily prepared and stable (±)-isopinocampheyldichloroborane [(±)-IpcBCl2] was conveniently used
for the stepwise hydroboration of two different alkenes using the in situ reduction−hydroboration
protocol to give mixed trialkylboranes, IpcBR1R2. Convenient elimination of α-pinene from these
trialkylboranes by treatment with an aldehyde, RCHO, provided the borinate ester, R1R2BOCH2R.
This intermediate was readily converted into the unsymmetrical ketones, R1COR2, in high yields
and purity, by an established method. This methodology was successfully applied to the synthesis
of enantiomerically pure spiroketals using optically pure TBS ether protected homoallylic alcohols
as the alkenes for stepwise hydroboration.