Alkene Addition of Frustrated P/B and N/B Lewis Pairs at the [3]Ferrocenophane Framework

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• 作者：Tanja Voss ; Jean-Baptiste Sortais ; Roland Fr枚hlich ; Gerald Kehr ; Gerhard Erker
• 刊名：Organometallics
• 出版年：2011
• 出版时间：February 14, 2011
• 年：2011
• 卷：30
• 期：3
• 页码：584-594
• 全文大小：1244K
• 年卷期：v.30,no.3(February 14, 2011)
• ISSN：1520-6041

文摘

o-Vinyl/伪-NRR鈥?substituted [3]ferrocenophane derivatives (R = R鈥?= Me (8), R = H, R鈥?= ^tBu (11), R = R鈥?= H (13)) were prepared via a Wittig olefination route starting from the corresponding aldehyde. The NMe₂ group was further exchanged for Pmes₂ (9). The bulky 伪-substituents NH^tBu and Pmes₂ form frustrated Lewis pairs with B(C₆F₅)₃ that undergo cooperative intramolecular addition reactions to the adjacent alkene. In the case of 13 stable Lewis pair adduct (14) formation is observed instead. The corresponding 伪-dimesitylphosphino[3]ferrocenophanyl-substituted butadiene (16) and acrolein (23) derivatives were synthesized via multistep synthetic pathways. Upon treatment with B(C₆F₅)₃, intramolecular 1,4-addition of the frustrated Lewis pairs to the adjacent doubly unsaturated moieties takes place to yield the zwitterionic products 17 and 24, respectively. The complexes 9, 10, 12, 16, 17, 20, 22, and 23 were characterized by X-ray diffraction.