We report an enantioselective palladium-catalyzed trans-hydroalkoxylation of propargylic amines with a trifluoroacetaldehyde-derived tether to build chiral oxazolidines. Diastereoselective hydrogenation using a heterogeneous palladium catalyst then gave access to protected benzylic amino alcohols in 45–87% yields and 84–94% ee values. Hydroalkoxylation of the alkynes required a catalytic amount of aryl iodide, highlighting the counterintuitive key role played by a putative Pd(II)/ArI oxidative addition complex to promote oxypalladation/protodemetalation.

中文翻译：

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钯催化的反式羟基烷氧基化：违反直觉地使用芳基碘添加剂促进 C-H 键形成

我们报告了一种对映选择性钯催化的炔丙胺与三氟乙醛衍生的链的反式氢化烷氧基化，以构建手性恶唑烷。使用非均相钯催化剂进行非对映选择性氢化，然后以 45-87% 的收率和 84-94% 的 ee 值获得受保护的苄基氨基醇。炔烃的氢化烷氧基化需要催化量的芳基碘，突出了推定的 Pd(II)/ArI 氧化加成络合物在促进氧化钯化/原脱金属化方面所起的违反直觉的关键作用。