Application of a Ferrocene-Based Palladacycle Precatalyst to Enantioselective Aryl-Aryl Kumada Coupling
Application of a Ferrocene-Based Palladacycle Precatalyst to Enantioselective Aryl-Aryl Kumada Coupling
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DOI：
10.1002/ejic.202101077
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发表时间：
2022-02-17
影响因子：
2.3
通讯作者：
Richards, Christopher J.
中科院分区：
文献类型：
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作者：
Arthurs, Ross A.;Hughes, David L.;Richards, Christopher J.
1-碘-2-甲基萘与2-甲基-1-萘基溴化镁在钯催化下反应，定量地得到了（S-a）构型的交叉偶联产物，其e.e.为80%。使用（R，S-p）-PPFA作为配体。将N，N-二甲基氨基甲基二茂铁环钯化（Na 2 PdCl 4，（S）-Ac-Phe-OH，93 % e.e.，作为自诱导的非等价性的结果，通过H-1 NMR测定），并将所得的（S-p）-构型的二聚钯配体用作该交叉偶联反应的预催化剂（5mol%）。将二苯基膦添加到钯配体中，随后进行碱促进的双齿配体合成和钯捕获，得到原位生成的催化剂，得到高达71% e. e的（S-p）-构型产物。
The palladium catalysed reaction of 1-iodo-2-methylnaphthalene and 2-methyl-1-naphthylmagnesium bromide gave quantitatively an (S-a)-configured cross-coupled product in 80 % e.e. using (R,S-p)-PPFA as a ligand. N,N-Dimethylaminomethylferrocene was cyclopalladated (Na2PdCl4, (S)-Ac-Phe-OH, 93 % e.e., as determined by H-1 NMR as a result of self-induced non-equivalence), and the resulting (S-p)-configured dimeric palladacycle was employed as a precatalyst for this cross-coupling reaction (5 mol%). Addition to the palladacycle of diphenylphosphine and subsequent base-promoted bidentate ligand synthesis and palladium capture gave an in situ generated catalyst resulting in an (S-p)-configured product in up to 71 % e.e.