Aqueous Asymmetric Mukaiyama Aldol Reaction Catalyzed by Chiral Gallium Lewis Acid with Trost-Type Semi-Crown Ligands

✍ Scribed by Hui-Jing Li; Hong-Yu Tian; Yan-Chao Wu; Yong-Jun Chen; Li Liu; Dong Wang; Chao-Jun Li

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 251 KB
• Volume: 347
• Category: Article
• ISSN: 1615-4150
• DOI: 10.1002/adsc.200505089

✦ Synopsis

Abstract

The combination of Ga(OTf)~3~ with chiral semi‐crown ligands (1a–e) generates highly effective chiral gallium Lewis acid catalysts for aqueous asymmetric aldol reactions of aromatic silyl enol ethers with aldehydes. A ligand‐acceleration effect was observed. Water is essential for obtaining high diastereoselectivity and enantioselectivity. The p‐phenyl substituent in aromatic silyl enol ether (2 h) plays an important role and increases the enantioselectivity up to 95% ee. Although aliphatic silyl enol ethers provided low enantioselectivities and silylketene acetal is easily hydrolyzed in aqueous alcohol, the aldol reactions of silylketene thioacetal (12) with aldehydes in the presence of gallium‐Lewis acid catalysts give the β‐hydroxy thioester with reasonable yields and high diastereo‐ (up to 99 : 1) and enantioselectivities (up to 96% ee).