Dehydrative Synthesis of Functionalized Skipped Dienes from Stabilized Phosphonium Ylides and Allylic Alcohols in Water

• Published in: Advanced synthesis & catalysis Vol. 361; no. 5; pp. 1023 - 1027
• Main Authors: Ma, Xiantao, Yu, Jing, Han, Cuijie, Zhou, Qiuju, Ren, Mengjuan, Li, Lixin, Tang, Lin
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 05.03.2019; Wiley Subscription Services, Inc
• Subjects: Alcohol; Alcohols; Alkylation; Allylic alcohols; Aromatic compounds; Chemistry; Chemistry, Applied; Chemistry, Organic; Dehydration; Dehydrative synthesis; Dienes; Hydrogen bond; Hydrogen bonds; NMR; Nuclear magnetic resonance; Physical Sciences; Regioselectivity; Science & Technology; Skipped dienes; Synthesis; Water media; PALLADIUM; SUBSTITUTION; ALKYLATION; AQUEOUS-MEDIA; BAYLIS-HILLMAN REACTION; CATALYZED ALLYLATION; STEREOSPECIFIC SYNTHESIS; Allylic alcohols; Dehydrative synthesis; BOND-CLEAVAGE; Water media; CROSS-COUPLING REACTIONS; STEREOSELECTIVE-SYNTHESIS; Skipped dienes; Hydrogen bond
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201801266

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.