Direct Catalytic Asymmetric Aldol Reaction of α‑Vinyl Acetamide

A direct catalytic asymmetric aldol addition of an α-vinyl 7-azaindoline amide to both aromatic and aliphatic aldehydes was promoted by a cooperative acid/base catalyst in a stereodivergent manner. The key structural element, a 7-azaindoline moiety, facilitated catalytic enolization, allowing for subsequent stereoselective aldol addition. Enantioselective synthesis of the key intermediate of blumiolide C and kainic acid supported the synthetic utility of this protocol.本工作以协同酸碱催化剂（cooperative acid/base catalyst）为催化体系，以立体发散模式实现了α-乙烯基7-氮杂吲哚啉酰胺（α-vinyl 7-azaindoline amide）与芳香醛、脂肪醛的直接催化不对称羟醛加成反应。该反应的关键结构单元7-氮杂吲哚啉（7-azaindoline moiety）可有效促进催化烯醇化过程，为后续的立体选择性羟醛加成反应奠定基础。通过对布鲁米内酯C（blumiolide C）与红藻氨酸（kainic acid）关键中间体的对映选择性合成，证实了该反应策略的合成应用价值。