Pd-Catalyzed Rearrangement of N-Alloc-N-allyl Ynamides via Auto-Tandem Catalysis: Evidence for Reversible C-N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement

被引：15

作者：

Alexander, Juliana R. ^{[1
]}

Shchepetkina, Veronika, I ^{[1
]}

Stankevich, Ksenia S. ^{[1
]}

Benedict, Rory J. ^{[1
]}

Bernhard, Samuel P. ^{[1
]}

Dreiling, Reagan J. ^{[1
]}

Cook, Matthew J. ^{[1
]}

机构：

[1] Montana State Univ, Dept Chem & Biochem, Bozeman, MT 59717 USA

来源：

ORGANIC LETTERS | 2021年 / 23卷 / 02期

关键词：

ONIOM; LIGANDS; ENERGY;

D O I：

10.1021/acs.orglett.0c04078

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An auto-tandem catalytic double allylic rearrangement of N-alloc-N-allyl ynamides was developed. This reaction proceeds through two separate and distinct catalytic cycles with both decarboxylative Pd-pi-allyl and Pd(0)-promoted aza-Claisen rearrangements occurring. A detailed mechanistic study supported by computations highlights these two separate mechanisms. Previously unreported reversible C-N ionization and a Pd(0)-catalyzed [3,3]-sigmatropic rearrangement were discovered. This study provides new reaction pathways for both pi-allyl and sigmatropic rearrangements.

引用

页码：559 / 564

页数：6

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