Thiourea‐catalyzed Oxidative Coupling Reaction of N‐Phenyl Tetrahydroisoquinoline with β‐Keto Acids

Applications of Bond Energy‐Based Thermodynamic Analysis to the Feasibility of Unfunctionalized C−C Cross‐Coupling Reactions

“…An initial observation of Proline catalyzed aldol reactions rapidly expanded in the last two decades into many actively pursued fields in organic synthesis [86] . Other organo‐catalysts like thiourea have also been used for cross‐coupling [87–89] and nucleophilic substitutions [87,90] . Nonetheless, there has been a sense of caution induced by the retraction of a Nature article reporting an amine‐catalyzed Suzuki‐Miyaura‐type coupling [91] .…”

Enantioselective Decarboxylative Alkylation of β-Keto Acids to ortho-Quinone Methides as Reactive Intermediates: Asymmetric Synthesis of 2,4-Diaryl-1-benzopyrans

“…However, the asymmetric alkylation reaction between o -QMs and β-keto acids has not been described. The decarboxylative reactions of β-keto acids as ketone enolate equivalents have received much attention due to their higher reactivity and regioselectivity . We therefore envisioned that in situ generated o -QMs A could probably react with β-keto acids via enantioselective decarboxylative alkylation to produce chiral Michael adduct B, followed by sequential formation of the hemiketals C and dehydration to give chiral 2,4-diaryl-1-benzopyrans (Scheme c).…”