10.1021/jo980432g.s001 Donald S. Matteson Donald S. Matteson Rajendra Prasad Singh Rajendra Prasad Singh Bonnie Schafman Bonnie Schafman Jing-jing Yang Jing-jing Yang Asymmetric Synthesis of Serricornin via Boronic Esters American Chemical Society 1998 hydrogen peroxide Asymmetric Synthesis methylmagnesium bromide sodium periodate osmium tetraoxide dichloromethyl carbon skeleton ethylethenylmagnesium cigarette beetle ethylmagnesium bromide DICHED Boronic Esters chain extensions stereoselective boronic ester chemistry 1998-06-05 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Asymmetric_Synthesis_of_Serricornin_via_Boronic_Esters/3711627 Highly stereoselective boronic ester chemistry has been used for the synthesis of (4<i>S</i>,6<i>S</i>,7<i>S</i>)-7-hydroxy-4,6-dimethylnonanone (<b>1</b>), the pheromone of the cigarette beetle. 2-Bromo-1-butene (<b>8</b>) was made from 1-butyne via bromoboration and protodeboronation, and was converted to 1-ethylethenylmagnesium bromide. (<i>R</i>,<i>R</i>)-1,2-Dicyclohexyl-1,2-ethanediol [“(<i>R</i>)-DICHED”] methylboronate was treated with (dichloromethyl)lithium to yield (<i>R</i>)-DICHED (<i>S</i>)-1-chloroethylboronate (<b>9</b>), which with 1-ethylethenylmagnesium bromide yielded (<i>R</i>)-DICHED (<i>R</i>)−(2-ethyl-1-methyl-2-propenyl)boronate (<b>10</b>). Further chain extensions with (chloromethyl)lithium, (dichloromethyl)lithium followed by methylmagnesium bromide, and (dichloromethyl)lithium followed by ethylmagnesium bromide completed assembly of the carbon skeleton. Deboronation with hydrogen peroxide yielded (3<i>S</i>,5<i>S</i>,6<i>S</i>)-2-ethyl-3,5-dimethylocten-6-ol (<b>14</b>), which with osmium tetraoxide and sodium periodate yielded <b>1</b>.