The first total synthesis of anominine has been achieved, and the absolute configuration of the product has been determined. The key features include the development of a new, highly efficient organocatalyzed method for the asymmetric synthesis of Wieland-Miescher ketone building blocks, an unusual selenoxide [2,3]-sigmatropic rearrangement, and a ZrCl(4)-catalyzed indole coupling as well as several chemoselective transformations controlled by the structurally congested nature of the bicyclic core.

The first convergent total synthesis of isobongkrekic acid is reported involving three different stereospecific palladium cross-couplings for the formation of the diene units. Access to bongkrekic acid by this route is also demonstrated. These syntheses involve the formation of several potentially general building blocks.

A highly efficient (93% overall yield) and enantioselective (94% ee) synthesis of the WielandMiescher ketone (10-g scale) through a solvent-free Robinson annulation procedure is reported. The process involves only 1 mol% triethylamine as the base in the initial Michael process and the organocatalyst N-tosyl-(S a )-binam-l-prolinamide (2 mol%) and benzoic acid (0.5 mol%) for the intramolecular aldol process. This green protocol is applied to a wide range of valuable building block analogues of the Wieland-Miescher ketone (10 examples). Among these, a noteworthy compound for terpene synthesis is the 8a-allyl derivative, which is prepared in 93% yield and 97% ee in a process allowing the recovery and reutilization of the organocatalyst. Furthermore, a one-pot, two-step process has also been developed.

A highly congested decalin embodying an alpha-methylene ketone is synthesized in 11 steps from the Wieland-Miescher ketone and efficiently converted to the polycyclic frameworks of anominine and tubingensin A, which constitutes the first approach to the skeleton of these indole diterpenoids.

( S )‐8a‐Methyl‐3,4,8,8a‐tetrahydro‐1,6(2 H ,7 H )‐naphtalenedione 2‐Methyl‐2‐(3‐oxobutyl)‐1,3‐cyclohexanedione 2‐Methyl‐1,3‐cyclohexanedione N ‐Tosyl‐( S a )‐binam‐L‐prolinamide Methyl vinyl ketone