Diastereomeric enzymatic (Chirazyme® L-2, c.−f., C2) resolution of 3-C-acetoxymethyl-1,2,3,4,5-pentadeoxy-6,7:8,9-di-O-isopropylidene-β-D-gluco- and -D-manno-dec-6-ulo-6,10-pyranose (6), obtained from “diacetone D-fructose aldehyde” (3) and the corresponding phosphorane from (3-benzyloxy-2-ethylpropyl)triphenylphosphonium iodide (2), has enabled us to synthesize spiroketals (3R,4S,5S,6R,9R)- and (3R,4S,5S,6R,9S)-9-ethyl-3,4-isopropylidenedioxy-1,7-dioxaspiro[5.5]undecane (7 and 8). An attempt to transform 8 into (−)-talaromycins G and 9-epi-A was unsuccessful. However, (−)-talaromycins C and E could be enantiospecifically prepared from spiroketal 7 in twelve steps.