原标题：康 · 学术 | Reaction of the Day No. 520

Ligand-controlled β-selective C(sp3)–H Arylation of N-Boc-piperidines

Anthony Millet,aPaolo Larini,aEric Clotband Olivier Baudoin*

aUniversit´e Claude Bernard Lyon, bInstitut Charles Gerhardt

— Chem. Sci. 4, 2241–2247 (2013)

Recommended by Ying Zhang

KEY WORDS: Palladium Catalyzed; β-Arylation; Boc-piperidines; 3-arylpiperidines; Ligand

ABSTRACT:The authors report a general palladium-catalyzed β-arylation of Boc-piperidines, which yields a variety of valuable 3-arylpiperidines in a simple and direct manner. The β- vs. α-arylation selectivity was controlled by the ligand, with flexible biarylphosphines providing mainly the desired β-arylated products whereas more rigid biarylphosphines mainly furnished the more classical α-arylated products. The computed reaction mechanism (DFT), studied from the common α-palladated intermediate, indicated that the reductive elimination steps leading to the α- and β-arylated products are electivity determining. Moreover, the experimental trend obtained with different ligands was well reproduced by the calculations.

Scope of the β-arylation of Boc-piperidine.

In conclusion, the authors have reported a general palladium-catalyzed β-arylation of Boc-piperidines, leading to a variety of valuable 3-arylpiperidines in a regioselective and highly diastereoselective manner. The β- vs. α-arylation selectivity was essentially controlled by the ligand, with fexiblebiarylphosphines providing the desired β-arylated products whereas more rigid biarylphosphines furnished the more classical α-arylated products. The extension of these results and mechanistic data to other synthetically relevant systems will be reported in due course.

作者报道了Boc-哌啶的钯催化的β-芳基化，从而以区域选择性和高度非对映选择性的方式产生了多种有价值的3-芳基哌啶。返回搜狐，查看更多

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