Efficient and practical synthesis of l-hamamelose

Abstract

An efficient synthetic route of l-hamamelose was successfully accomplished starting from d-ribose. l-Hamamelose was synthesized in 42% overall yield with six reaction steps via a stereoselective Grignard reaction, a stereoselective crossed aldol reaction and a controlled oxidative cleavage of the double bond of a vinyl diol compound. During the oxidative cleavage of the double bond of the vinyl diol compound with osmium tetroxide and NaIO 4, an over-oxidative cleavage of α-hydroxyl aldehyde generated from ring opening of the first cleaved product, formyl lactol, did not occur, probably due to the stability of the lactol form. A plausible mechanism for the stereoselective crossed aldol reaction was suggested. The final target compound, l-hamamelose can play a very important role as a chiral building block in synthesizing a wide variety of enantiopure compounds. © 2009 Elsevier Ltd. All rights reserved.