通过1,2- c /Pd（IV）异向重排，Pd(II)/ pida使末端烯烃迁移三重功能化。

IF 16.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI:10.1002/anie.202518735

Chen-Xu Liu,Qian Wang,Jieping Zhu

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引用次数: 0

摘要

我们报道了Pd（II）催化的末端烯烃的迁移三重功能化。在Pd（II）催化下，同烯丙基酰胺与苯二乙酸（III）二酯（PIDA）的反应通过形成1个C─C和2个C─O键生成6-乙酰化的5,6-二氢- 4h -1,3-恶嗪。机理研究表明，这一过程包括氧化、Pd（II）氧化为Pd（IV）、1,2-烷基（芳基）/Pd（IV）异向重排（DR）以及随后的乙酰氧基化。虽然PIDA作为氧化剂的Pd(II)/Pd（IV）催化已经实现了许多强大的转化，但这里报道的DR是前所未有的。

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Pd(II)/PIDA-Enabled Migratory Triple Functionalization of Terminal Alkenes via a 1,2-C/Pd(IV) Dyotropic Rearrangement.

We report a Pd(II)-catalyzed migratory triple functionalization of terminal alkenes. The reaction of homoallylic amides with phenyliodine(III) diacetate (PIDA) under Pd(II) catalysis delivers 6-acetoxylated 5,6-dihydro-4H-1,3-oxazines through the formation of one C─C and two C─O bonds. Mechanistic studies suggest a sequence involving oxypalladation, oxidation of Pd(II) to Pd(IV), a 1,2-alkyl(aryl)/Pd(IV) dyotropic rearrangement (DR), and subsequent acetoxylation. While Pd(II)/Pd(IV) catalysis with PIDA as the oxidant has enabled numerous powerful transformations, the DR reported here is unprecedented.

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来源期刊

Angewandte Chemie International Edition 化学-化学综合

CiteScore

26.60

自引率

6.60%

发文量

3549

审稿时长

1.5 months

期刊介绍： Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.