Synthesis of Enantiomerically and Diastereomerically Pure 4-Hydroxy-1,2-alkadienyl Carbamates and Their Application in a Modified Nazarov Cyclization Towards Chiral Cyclopentenones

Abstract

The addition of racemic titanated alkynyl N,N-diisopropylcarbamates onto enantiopure α-dibenzylamino- or α-silyloxy­alkanals affords two (out of four possible) diastereomeric, enantiopure 5-hetero-substituted 4-hydroxy-1,2-alkadienyl carbamates. As demonstrated for hydroxyallenes 23 and 24, the reaction sequence for modified Nazarov cyclization according to Tius, yields stereohomogeneous, highly substituted 5-alkylidene-2,3-dialkyl-4-phenyl-2-cyclopenten-1-ones (Z,R)-25 and (E,R)-26.

diastereoselectivity - allenes - Nazarov reactions - carbamates - cyclizations - cyclopentenones

References

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X-ray structure analysis.

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Yields of compound (Z,R)-25 and (Z,R)-26 are based on enone 20a.