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An enantioselective Michael addition of malonates to α,β-unsaturated para-nitrophenyl esters was achieved using the Lewis basic isothiourea HyperBTM, giving excellent levels of product enantioselectivity (up to >99:1 enantiomeric ratio) in good yields and with complete regioselectivity (>20:1 regioselectivity ratio) in the presence of alternative (phenyl ketone and ethyl ester) Michael acceptors. Density functional theory calculations indicate that N-acylation is rate-limiting. This constitutes a rare example of a highly enantioselective addition of simple, readily available malonates to α,β-unsaturated esters.

A straightforward methodology for the decarboxylative cross‐coupling of aryl bromides and phenylpropiolic acid using a Pd(II)‐NHC catalyst has been developed. Various aryl bromides have been successfully transformed into the corresponding di‐substituted alkynes using environmentally benign conditions (weak base and ethanol as solvent). This efficient catalytic system also proved useful for the copper‐free Sonogashira coupling of aryl and alkenyl bromides with various terminal alkynes. The synthetic utility of these methodologies was highlighted in the synthesis of a polyaromatic compound and various fluoroenynes.

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