Phosphine‐Catalyzed Activation of Alkylidenecyclopropanes: Rearrangement to Form Polysubstituted Furans and Dienones. Issue 31 (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 international edition. Volume 58:Issue 31(2019)
• Page Start: 10698
• Page End: 10702
• Publication Date: 2019-06-27
• Subjects: dienones -- furans -- organocatalysis -- phosphines -- rearrangement; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201903320
• Languages: English
• ISSNs: 1433-7851

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 : One to three : Phosphine‐catalyzed activation of alkylidenecyclopropanes (ACPs) generates allylic phosphonium intermediates that resemble the well‐studied phosphine‐allene adducts but exhibit distinct properties. These intermediates facilitate three types of rearrangements to form polysubstituted furans and dienones.