Phosphine‐Catalyzed Activation of Alkylidenecyclopropanes: Rearrangement to Form Polysubstituted Furans and Dienones. (27th June 2019)

• Record Type: Journal Article
• Authors: He, Xin; Tang, Yuhai; Wang, Yongzhuang; Chen, Jian‐Bo; Xu, Silong; Dou, Jianwei; Li, Yang
• Is Part Of: Angewandte Chemie. Volume 131:Number 31(2019)
• Page Start: 10808
• Page End: 10812
• Publication Date: 2019-06-27
• Subjects: Dienone -- Furane -- Organokatalyse -- Phosphine -- Umlagerung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201903320
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: We report a phosphine‐catalyzed ring opening of electron‐deficient alkylidenecyclopropanes (ACPs) to generate allylic phosphonium zwitterions that resemble the well‐studied phosphine‐allene adducts but exhibit distinct properties. The potent reactivity of these intermediates has been demonstrated in three types of substrate‐controlled phosphine‐catalyzed rearrangements of alkylidenecyclopropylketones, which chemoselectively afford tri‐ and tetrasubstituted furans, and trisubstituted dienones in good yields. Abstract : Eins zu drei : Die phosphorkatalysierte Aktivierung von Alkylidencyclopropanen (ACPs) erzeugt allylische Phosphonium‐Intermediate, die den gut untersuchten Phosphin‐Allen‐Addukten ähneln, aber andere Eigenschaften aufweisen. Diese Intermediate ermöglichen drei Arten von Umlagerungen zur Bildung von polysubstituierten Furanen und Dienonen.