Shanghai Key Laboratory of Green Chemistry and Chemical, Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N. Zhongshan Road, Shanghai, 200062, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2017 Dec 11;56(50):15905-15909. doi: 10.1002/anie.201709595. Epub 2017 Nov 20.
Highly enantioselective gold-catalyzed intramolecular cyclization of N-allenamides was implemented by utilizing a designed chiral sulfinamide phosphine ligand (PC-Phos). This represents the first example of highly enantioselective intramolecular cyclization of N-allenamides. The practicality of this reaction was validated in the total synthesis of (R)-desbromoarborescidine A and formal synthesis of (R)-desbromoarborescidine C and (R)-deplancheine. Moreover, the catalyst system PC-Phos/AuNTf proved to be specifically efficient to promote the desymmetrization of N-allenamides in excellent yields with satisfactory ee values.
通过使用设计的手性亚砜酰胺膦配体（PC-Phos），实现了高对映选择性的金催化 N-烯丙酰胺的分子内环化反应。这代表了首例高对映选择性的 N-烯丙酰胺分子内环化反应。该反应的实用性在（R）-去溴阿尔博斯丁 A 的全合成和（R）-去溴阿尔博斯丁 C 和（R）-去普兰辛的形式合成中得到了验证。此外，催化剂体系 PC-Phos/AuNTf 被证明能够特异性地有效地促进 N-烯丙酰胺的去对称化，以优异的收率和令人满意的 ee 值得到目标产物。
