A convenient synthesis of gamma-functionalized cyclopentenones.

The synthesis of gamma-functionalized cyclopentenones was carried out in a few steps, starting firstly with the preparation of nitroketonic intermediates 2, which were readily transformed into 1,4-diketones using the Nef conversion. The intramolecular cyclization of the gamma-diketones 3 in a basic medium, led to the functionalized cyclopentenones 4.

Exclusive alpha-coupling in the aldol reaction of unsaturated trimethylsilyl esters: an efficient and practical direct synthesis of unsaturated beta-hydroxy acids.

The lithium enolates of trimethylsilyl but-3-enoate and 3-methylbut-3-enoate reacted with aldehydes and saturated or aromatic ketones at -70 degrees C to give exclusively the alpha-condensation products in excellent yields. The unsaturated beta-hydroxy acids thus obtained were directly identified, and the usual conversion into their methyl esters with diazomethane was not necessary. Unsaturated ketones underwent Michael reaction through alpha-addition leading to the unsaturated 5-oxo acids.