Phosphine‐Catalyzed Activation of Alkylidenecyclopropanes: Rearrangement to Form Polysubstituted Furans and Dienones

• Published in: Angewandte Chemie International Edition Vol. 58; no. 31; pp. 10698 - 10702
• Main Authors: He, Xin, Tang, Yuhai, Wang, Yongzhuang, Chen, Jian‐Bo, Xu, Silong, Dou, Jianwei, Li, Yang
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 29.07.2019; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Adducts; Allene; Chemistry; Chemistry, Multidisciplinary; dienones; Furans; Intermediates; organocatalysis; Pesticides; Phosphine; phosphines; Physical Sciences; rearrangement; Ring opening; Science & Technology; Substrates; Zwitterions; phosphines; ALPHA,BETA-UNSATURATED IMINES; CYCLOPROPYL KETONES; RING EXPANSION; dienones; ACRYLAMIDE-TETHERED ALKYLIDENECYCLOPROPANES; BAYLIS-HILLMAN ACETATES; 3+2 CYCLOADDITION; organocatalysis; 4+2 ANNULATION; FACILE SYNTHESIS; DELTA-ACETOXY ALLENOATES; furans; STEREOSELECTIVE-SYNTHESIS; rearrangement

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...