An inexpensive and air-stable organo-manganese auxiliary (MMD) can be complexed to alkynes followed by isomerization to afford uniquely stable η<sup>2</sup>-complexed MMD-allenyl aldehydes. In this presentation, we report nucleophilic additions to these MMD complexes with several organometallic reagents leading to highly substituted allenyl alcohols as single diastereomers in most cases. The MMD auxiliary amplifies the directing effect of distant γ-substituents and is removed under mild oxidation conditions. To highlight the utility of these substituted allenyl alcohols in complex synthesis the current method was also used to prepare a nitrile-substituted allenol in high diastereoselectivity. This allenol was then converted to Hagen's gland lactone in four additional steps. Preliminary studies will also be present showing that non-racemic MMD-complexed allenyl aldehydes can be conveniently prepared under chiral phase transfer catalyzed (PTC) conditions.

Stereoselective synthesis of allenyl alcohols using an organo-manganese η<sup>2</sup>-auxiliary: A new entry to furofuranone natural products

249th National Meeting (2015)

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Stereoselective synthesis of allenyl alcohols using an organo-manganese η2-auxiliary: A new entry to furofuranone natural products

Stereoselective synthesis of allenyl alcohols using an organo-manganese η²-auxiliary: A new entry to furofuranone natural products