The first synthesis of coprinol has been achieved from 2-methoxy-3,5-dimethylbenzaldehyde via the intermediacy of an indanone derivative where dialkylation, Friedel-Crafts acylation, demethylation, and regioselective formation of a primary -OH group from a chloroacetyl group are the key steps.
The total synthesis of the phenolic sesquiterpene onitin using dimethylated indanone as the key intermediate is reported. Key to the success of this synthesis route is the Suzuki-Miyaura cross-coupling reaction of aryl bromide to introduce the vinyl side chain followed by formyl selective Wacker oxidation to generate the aldehyde. The target aldehyde was also obtained in high overall yield via an acid-catalyzed pinacol-pinacolone-type rearrangement of the epoxide. The epoxide was generated from oxidation of a styrene derivative by oxone. Demethylation of the aldehyde followed by chemoselective reduction furnished onitin.
A general stereoselective route to functionalized and substituted tricyclo [5.2.2.0(1,5)]undecenones, tricyclo[6.2.2.0(1,6)]dodecenones, and [3.3.3]- and [4.3.3]propellanes from simple aromatic precursors is reported. The methodology involves generation and cycloaddition of annulated cyclohexa-2,4-dienones with various acrylates followed by manipulation of the resulting tricyclic adducts, leading to functionalized tricyclo[5.2.2.0(1,5)]undecenones and tricyclo[6.2.2.0(1,6)]dodecenones endowed with a beta,gamma-enone chromophore. Photochemical reaction of the tricyclic chromophoric systems followed by reductive cleavage provided an efficient entry into propellanes.
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