Rigamonti Marco Giulio, Gatti Francesco Gilberto
Chemistry Department "G. Natta", Politecnico di Milano, Piazza Leonardo da Vinci 1, 20133 Milano, Italy.
Beilstein J Org Chem. 2015 Nov 5;11:2117-24. doi: 10.3762/bjoc.11.228. eCollection 2015.
The first stereoselective synthesis of lippidulcines A, B and C has been accomplished starting from (+)-hernandulcin, which has been prepared on a multigram scale. The previously assigned absolute configurations have been confirmed. The key steps of this synthesis are based on a modified version of the Kornblum-DeLaMare rearrangement, and on a highly regioselective and stereoselective ketone reduction with the MeCBS reagent. The taste evaluations indicate that none of these sesquiterpenes are sweet, instead the lippidulcine A is a cooling agent with a mint after taste.
已从（+）-hernandulcin出发，首次完成了脂甜菊素A、B和C的立体选择性合成，（+）-hernandulcin已实现克级规模制备。先前指定的绝对构型已得到确认。该合成的关键步骤基于改良版的科恩布卢姆-德拉马尔重排，以及使用MeCBS试剂进行的高度区域选择性和立体选择性酮还原反应。味觉评估表明，这些倍半萜均无甜味，相反，脂甜菊素A是一种具有薄荷后味的清凉剂。
