Construction of tetrahydrofurans by PdII/PdIV-catalyzed aminooxygenation of alkenes
Construction of tetrahydrofurans by PdII/PdIV-catalyzed aminooxygenation of alkenes
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DOI：
10.1002/anie.200701454
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Sanford, Melanie S.
中科院分区：
文献类型：
--
作者：
Desai, Lopa V.;Sanford, Melanie S.
PdII α-烷基或α-芳基中间体的催化转化在有机合成中有着广泛的应用，并为许多有价值的产物的合成提供了有吸引力的途径。[1]然而，这些反应中的绝大多数通过Pd 0/PdII机制进行。因此，可以构建的结构/键的多样性受到这种氧化还原循环的限制。最近的研究已经探索了在强氧化剂（例如，PhI（0Ac）2、过硫酸氢钾、N-卤代琥珀酰亚胺、碘）存在下PdII σ烷基/芳基物质的生成，以获得替代的PdII/PdIV反应歧管。[2-4]重要的是，这些氧化转化通常产生与传统Pd 0/II催化形成的有机产物高度互补的有机产物。[2-4]我们的团队对利用PdII/PdIV催化循环开发新的有机转化感兴趣。[2a-e作为这些努力的一部分，我们推断PdII β氨基烷基物质（由烯烃的氨基钯化产生）[5]可能被PhI（OAc）2氧化拦截（方案1）。如果成功的话，这样的反应将提供一个有吸引力的PdII/PdIV催化的路线，从烯烃到氨基，
Catalytic transformations involving PdII σ-alkyl or σ-aryl intermediates are widely used in organic synthesis and offer attractive routes to many valuable products.[1] However, the vast majority of these reactions proceed by Pd0/PdII mechanisms. As a result, the diversity of structures/bonds that can be constructed is constrained by the limitations of this redox cycle. Recent studies have explored the generation of PdII σalkyl/aryl species in the presence of strong oxidants (eg, PhI (OAc) 2, oxone, N-halosuccinimides, iodine) to access alternative PdII/PdIV reaction manifolds.[2–4] Importantly, these oxidative transformations often yield highly complementary organic products to those formed by traditional Pd0/II catalysis.[2–4]Our group is interested in exploiting PdII/PdIV catalytic cycles for the development of new organic transformations.[2a–e, 4a] As part of these efforts, we reasoned that PdII βaminoalkyl species (generated by the aminopalladation of olefins)[5] might be oxidatively intercepted with PhI (OAc) 2 (Scheme 1). If successful, such reactions would provide an attractive PdII/PdIV-catalyzed route from alkenes to amino-