Exploiting the Chiral Ligands of Bis(imidazolinyl)- and Bis(oxazolinyl)thiophenes—Synthesis and Application in Cu-Catalyzed Friedel–Crafts Asymmetric Alkylation

Five new C2-symmetric chiral ligands of 2,5-bis(imidazolinyl)thiophene (L1–L3) and 2,5-bis(oxazolinyl)thiophene (L4 and L5) were synthesized from thiophene-2,5-dicarboxylic acid (1) with enantiopure amino alcohols (4a–c) in excellent optical purity and chemical yield. The utility of these new chiral ligands for Friedel–Crafts asymmetric alkylation was explored. Subsequently, the optimized tridentate ligand L5 and Cu(OTf)2 catalyst (15 mol%) in toluene for 48 h promoted Friedel–Crafts asymmetric alkylation in moderate to good yields (up to 76%) and with good enantioselectivity (up to 81% ee). The bis(oxazolinyl)thiophene ligands were more potent than bis(imidazolinyl)thiophene analogues for the asymmetric induction of the Friedel–Crafts asymmetric alkylation.

Enantioselective C–H Alkylation of N-Arylbenzamides with Vinyl Ethers Catalyzed by an Iridium/Chiral Phosphoramidite–Olefin Complex

Chiral phosphoramidite−olefin hybrid ligands were found to be effective in the iridium-catalyzed asymmetric alkylation of N-arylbenzamides with vinyl ethers. The reaction was catalyzed by a hydroxoiridium catalyst coordinated with the hybrid ligand to give the corresponding products in high yields with high branch- and enantioselectivity.

Stereodivergent Pd/Cu catalysis: asymmetric alkylation of racemic symmetrical 1,3-diphenyl allyl acetates

A stereodivergent Pd/Cu catalyst system was developed, which was successfully applied to the asymmetric allylic alkylation of symmetrical 1,3-disubstituted allyl acetates with prochiral imino esters in a fully stereodivergent manner.