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>.