Dehydrative Synthesis of Functionalized Skipped Dienes from Stabilized Phosphonium Ylides and Allylic Alcohols in Water. Issue 5 (23rd January 2019)

• Record Type: Journal Article
• Authors: Ma, Xiantao; Yu, Jing; Han, Cuijie; Zhou, Qiuju; Ren, Mengjuan; Li, Lixin; Tang, Lin
• Is Part Of: Advanced synthesis & catalysis. Volume 361:Issue 5(2019)
• Page Start: 1023
• Page End: 1027
• Publication Date: 2019-01-23
• Subjects: Skipped dienes -- Dehydrative synthesis -- Allylic alcohols -- Water media -- Hydrogen bond; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201801266
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: A mild and extra activator‐free dehydrative alkylation of stabilized phosphonium ylides with allylic alcohols in water is developed in the presence of [Pd(allyl)Cl]2 /dppf catalyst. A wide range of aryl, heteroaryl, alkyl and even allylic tertiary alcohols can readily react with stabilized phosphonium ylides with high regioselectivity for the efficient synthesis of functionalized skipped dienes in moderate to high yields. The role of water was investigated by means of a high‐resolution mass spectrum and diffusion‐ordered spectroscopy nuclear magnetic resonance, and the results revealed that water might play a crucial role in the formation of the π‐allylpalladium complex via hydrogen bond. However, the present method is not suitable for water‐sensitive phosphonium ylides. Abstract :