The Rh(III)-catalyzed asymmetric reduction of α-trifluoromethyl ketones through transfer hydrogenation was developed under mild conditions to access a series of enantioenriched cistrifluoromethyl alcohols via a dynamic kinetic resolution process. The reaction was efficiently performed in the green solvent 2-MeTHF with HCO 2 H/Et 3 N (1 : 1) as the hydrogen source. High yields, alongside excellent diastereo-and enantioselectivities were obtained for the synthesis of CF 3 -chromanol, CF 3 -indanol and CF 3 -tetralol derivatives.

A protocol for the isothiourea-catalyzed enantioselective functionalization of pyrrolyl-and indolylacetic acids has been developed. Stereodefined dihydropyridinones are accessed through formal [4 + 2] cycloaddition of an in situ generated isothiouronium enolate with α,βunsaturated ketimines. The dihydropyridinones are obtained in moderate to excellent yield (26-97%), excellent diastereocontrol (all > 95 : 5 dr) and moderate to excellent enantiocontrol (75 : 25-99 : 1 er). An unusual elimination of pyrrole or indole from the dihydropyridinone to access achiral pyridinones was observed and could be selectively promoted. A further one-pot synthesis using an acyl imidazole was developed to give pyridinones in good to excellent yields (67-91%).

A straightforward method to access novel families of enantioenriched cis-monofluorinated carbocyclic alcohols has been developed through ATH/DKR in up to 97 % yield, up to 99 : 1 dr and enantioinductions up to 97 % ee. Trans-difluorinated indans, tetrahydronaphthalenes, tetrahydroquinolines and chromans have been synthesized as well by deoxofluorination of the corresponding cis-fluoro alcohols. The reaction was performed on a series of variously substituted 3-fluorochromanols, 3-fluorotetrahydroquinolinols, 2-fluoro inden-1-ols and 2-fluoro 1,2,3,4-tetrahydronaphthalen-1-ols in up to 86 % yields, with diastereoselectivities up to 97 : 3 and enantioselectivities up to > 99 % ee.

The preparation of functionalized 1,3-enynes bearing an acetal moiety at the 2-position has been studied through Sonogashira reaction of bromovinyl acetals with various alkyl- and aryl-substituted terminal alkynes.