Stereoselective Electrophilic α-Alkynylation of α,α-Disubstituted N-tert-Butanesulfinyl Ketimines for Construction of Less Accessible Acyclic Quaternary Stereocenters,Organic Letters

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Stereoselective Electrophilic α-Alkynylation of α,α-Disubstituted N-tert-Butanesulfinyl Ketimines for Construction of Less Accessible Acyclic Quaternary Stereocenters
Organic Letters ( IF 4.9 ) Pub Date : 2022-12-07 , DOI: 10.1021/acs.orglett.2c03865
Li-Feng Chu ₁ , Yun Yao ₁ , Chong-Dao Lu ₁

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In order to construct less accessible acyclic quaternary stereocenters, a protocol was developed to α-alkynylate α,α-disubstituted N-tert-butanesulfinyl ketimines stereoselectively using 1-(2-trimethylsilylethynyl)-1,2-benziodoxol-3(1H)-one in the presence of fluoride. Despite the steric and electrical similarity between the two α-substituents, the entire reaction proceeded in a strongly stereoselective manner: tBuOK promoted α-deprotonation of the acyclic ketimine to generate stereodefined fully substituted aza-enolates, which stereoselectively formed C–C bonds with electrophilic alkynylation reagents, affording α-alkynylation products with excellent stereocontrol.

中文翻译：

α,α-二取代的 N-叔丁基亚磺酰基酮亚胺的立体选择性亲电 α-炔基化，用于构建不易接近的无环季立体中心

为了构建不易接近的无环季立体中心，开发了一种方案，使用 1-(2-trimethylsilylethynyl)-1,2-benziodoxol-3(1 H )对 α-炔基化 α,α-二取代的N -叔丁亚磺酰基酮亚胺进行立体选择性- 一个在氟化物存在的情况下。尽管两个 α- 取代基之间存在空间和电学相似性，但整个反应以强烈的立体选择性方式进行：t BuOK 促进无环酮亚胺的 α- 去质子化以生成立体定义的完全取代的氮杂烯醇化物，其立体选择性地与亲电炔基化试剂，提供具有优良立体控制的α-炔基化产物。

更新日期：2022-12-07

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