Metallapentalenofuran: Shifting Metallafuran Rings Promoted by Substituent Effects. Issue 54 (4th September 2018)

• Record Type: Journal Article
• Authors: Hua, Yuhui; Lan, Qing; Fei, Jiawei; Tang, Chun; Lin, Jianfeng; Zha, Hexukun; Chen, Shiyan; Lu, Yinghua; Chen, Jiangxi; He, Xumin; Xia, Haiping
• Is Part Of: Chemistry. Volume 24:Issue 54(2018)
• Page Start: 14531
• Page End: 14538
• Publication Date: 2018-09-04
• Subjects: carbolong -- metallaaromatics -- metallafurans -- osmium -- reaction mechanism -- steric hindrance; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201802928
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Bulky substituents play important roles in controlling the reaction pathways or producing selected products. This work reports that the shift of metallafuran rings in a metallapentalenofuran complex can be promoted by the substituent effect via a reversible C−H bond reductive elimination and oxidative addition. The starting osmapentalyne, a so‐called 7‐carbon carbolong complex, was produced by the oxidation of a metallapentalenofuran with FeCl3 . It was then allowed to react with nucleophiles, followed by a C−H activation, to give the aforementioned metallapentalenofuran complex. This work enriches the family of carbolong complexes and reveals a new strategy to promote, but not prevent reactions by the bulky substituents. Abstract : Metallaaromatics : Treatment of metallapentalenofuran with FeCl3 in air quickly produces osmapentalyne, which can undergo a further nucleophilic reaction followed by a C−H activation to give metallapentalenofuran. The stereochemistry of its substituents dominates an interesting metallafuran ring shift under basic conditions (see scheme).