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Jeffrey D. Sears Salvador B. Muoz Stephanie L. Daifuku Ari A. Shaps Stephanie H. Carpenter William W. Brennessel Michael L. Neidig 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(9):2795-2799
The effects of β‐hydrogen‐containing alkyl Grignard reagents in simple ferric salt cross‐couplings have been elucidated. The reaction of FeCl3 with EtMgBr in THF leads to the formation of the cluster species [Fe8Et12]2?, a rare example of a structurally characterized metal complex with bridging ethyl ligands. Analogous reactions in the presence of NMP, a key additive for effective cross‐coupling with simple ferric salts and β‐hydrogen‐containing alkyl nucleophiles, result in the formation of [FeEt3]?. Reactivity studies demonstrate the effectiveness of [FeEt3]? in rapidly and selectively forming the cross‐coupled product upon reaction with electrophiles. The identification of iron‐ate species with EtMgBr analogous to those previously observed with MeMgBr is a critical insight, indicating that analogous iron species can be operative in catalysis for these two classes of alkyl nucleophiles. 相似文献
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