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.

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，在温和条件下产生脱芳烃 2-氧杂-7-氮杂[4.5]癸烷衍生物。该工艺包括从现成的烯酰胺中生成呋喃衍生的氮杂烯，然后用乙烯基苯并恶氮醌脱羧的 Pd-π-烯丙基偶极子进行 [2+4] 环加成反应。我们的方法有效地构建了螺[4.5]癸烷骨架，在 34 个实例中实现了 31-97% 的产率和非对映选择性从 6：1 dr 到 >20：1 dr。本研究引入了氮二烯作为 1,2-偶极子的新环加成位点，并为构建 oxa-azaspiro[4.5]癸烷框架提供了一种可靠的方法。