Sterically hindered substrates can be employed in an enantioselective palladium-catalyzed α-arylation with the chiral monophosphorus ligand BI-DIME. This process enabled an efficient synthesis of the antidepressant (S)-nafenodone, a four-step enantioselective synthesis of the Sceletium alkaloid (+)-sceletium A-4, a concise five-step enantioselective synthesis of (-)-corynoline, as well as a three-step preparation of (-)-DeN-corynoline.
A diastereo- and enantio-selective domino Michael-cyclization-tautomerization reaction of isatylidene malononitriles with α,α-dicyanoalkenes catalyzed by a cinchona alkaloid-derived bifunctional thiourea catalyst has been developed. A series of multi-functionalized spiro oxindole diene derivatives have been obtained in good to excellent yields (up to 97%) with good to excellent enantioselectivities (up to 96%) as well as good diastereoselectivities (up to 7.9 : 1). In addition, an anomalous temperature effect on the enantioselectivity has also been studied for this transformation.
The spirocyclic pyrazolones are an important class of molecular structures with significant biological and pharmaceutical activities. Herein, we demonstrate that the combination of a Cinchonabased chiral primary amine and an ortho-fluorobenzoic acid is an efficient catalyst system for the double Michael addition of arylidenepyrazolones with a,b-unsaturated ketones, providing chiral unsymmetrical 6,10-diaryl-substituted spiro[cyclohex-A C H T U N G T R E N N U N G anone-pyrazolone] derivatives in high yields (up to 98%) with good diastereoselectivities and excellent enantioselectivities (up to 88:12 dr, 99% ee).
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