Synthesis of Spiro Bis-Indanes via Domino Stetter-Aldol-Michael and Stetter-Aldol-Aldol Reactions: Scope and Limitations

Abstract

The synthesis of spiro bis-indanes by means of N-heterocyclic carbene (NHC) catalysis is reported. The dimerization of various o-formylchalcone substrates or their combination with phthaldialdehyde derivatives under the catalysis of thiazolium-derived­ carbenes afforded Stetter-aldol-Michael products and Stetter­-aldol-aldol products, respectively. The use of poor Michael acceptors in conjunction with an N-alkyltriazolium-derived catalyst furnished a variety of dibenzo[8]annulene products. This work highlights the interplay of a variety of factors affecting competing pathways in NHC-catalyzed domino reactions.

Key words

NHC - organocatalysis - Stetter - umpolung - domino reactions - Michael - aldol

References

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10

The reaction of 16c to produce 19c was performed with catalyst 11.

11

HPLC analysis on a chiral stationary phase showed 19a to be racemic even when the reaction was performed with weaker bases to avoid racemization.

13

The relative configuration for 21 and 21′ was determined by the coupling constants of the proton α to the carbonyl at δ = 5.91 (d, J = 8.8 Hz) for the major diastereomer and δ = 5.97 (d, J = 5.1 Hz) for the minor diastereomer.