Abstract β-Lithiated functionally substituted acrylates 2a–c prove to be versatile building blocks for spirotetronate syntheses useful in top half syntheses of the aglycon chlorothricolide 1 of the macrolide antibiotic chlorothricin. The electrophilic-nucleophilic cyclohexanone derivatives 27-cis/trans (with relative cis or trans relationship of the carboxylate group) required in this synthesis design are obtained via a cycloaddition route ...