We present a diastereoselective Au/Pd relay catalytic tandem cyclization reaction to produce dearomatic 2‐oxa‐7‐azaspiro[4.5]decane derivatives under mild conditions. This process involves generating furan‐derived azadiene from readily available enynamide, followed by a [2 + 4] cycloaddition with Pd‐π‐allyl dipole decarboxylated from vinyl benzoxazinanone. Our method efficiently constructs the spiro[4.5]decane skeleton, achieving yields ranging from 31‐97% and diastereoselectivities from 6:1 dr to >20:1 dr across 34 examples. This research introduces new cycloaddition sites for azadienes as 1,2‐dipoles and offers a reliable approach for constructing oxa‐azaspiro[4.5]decane frameworks.

中文翻译：

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通过金和钯中继催化烯炔酰胺与乙烯基苯并恶嗪酮的串联环化非对映选择性合成脱芳香2-氧杂-7-氮杂螺[4.5]癸烷衍生物


我们提出了一种非对映选择性 Au/Pd 中继催化串联环化反应，在温和条件下生产脱芳香族 2-氧杂-7-氮杂螺[4.5]癸烷衍生物。该过程涉及从容易获得的烯酰胺生成呋喃衍生的氮杂二烯，然后与乙烯基苯并恶嗪酮脱羧的 Pd-π-烯丙基偶极子进行 [2 + 4] 环加成。我们的方法有效地构建了螺[4.5]癸烷骨架，在 34 个示例中实现了 31-97% 的产率和从 6:1 dr 到 >20:1 dr 的非对映选择性。这项研究引入了氮杂二烯作为 1,2-偶极子的新环加成位点，并为构建 oxa-azaspiro[4.5]癸烷框架提供了可靠的方法。