Nitro Ketones in Organic Synthesis: A New, Short Synthesis of Racemic trans ‐2‐methyl‐1,7‐dioxaspiro[5.5]undecane, trans, trans‐ and trans , cis ‐2,8‐dimethyl‐1,7‐dioxaspiro[5.5]undecane by Henry reaction

The synthesis of spiroketals from nitro ketones is described. Racemic trans ‐2‐Methyl‐1,7‐dioxaspiro[5.5]undecane ( 1a ), and 2,8‐dimethyl‐1,7‐dioxaspiro[5.5]undecane ( 1b ) are synthesized as a mixture of trans , trans and trans , cis isomers in a ratio of 6.5:3.5 (separable by flash chromatography) by nitroaldol reaction (Henry reaction) of 6‐nitro‐2‐hexanone ( 2 ) with THP‐protected hydroxy aldehydes 3 on Amberlyst A21. Subsequent dehydration of the obtained nitro alkanols 4 with Ac 2 O/DMAP affords the nitro alkenes 5 which can be directly converted into 1 by sodium tetrahydridoborate reduction, and refluxing of the reaction mixture after acidification with 2 N HCl.