H‐*BEA Zeolite‐Catalyzed Nucleophilic Substitution in Allyl Alcohols Using Sulfonamides, Amides, and Anilines. Issue 28 (16th July 2020)

• Record Type: Journal Article
• Authors: Ohtsuki, Akimichi; Aoki, Shunsuke; Nishida, Ryo; Morita, Sachiko; Fujii, Takeshi; Okumura, Kazu
• Is Part Of: European journal of organic chemistry. Issue 28(2020)
• Page Start: 4309
• Page End: 4318
• Publication Date: 2020-07-16
• Subjects: Allyl alcohols -- Amidation -- Heterogeneous catalysis -- Zeolites -- Synthesis design; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202000296
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Herein, we report a novel zeolite‐catalyzed nucleophilic substitution in allyl alcohols. The product yield was improved upon the addition of NaOTf (0.05 mol‐%) using the studied zeolites. The highest yields were observed using H‐*BEA(Si/Al2 = 40)/NaOTf. The scope of the reaction with respect to the nucleophile was examined using 1, 3‐diphenylprop‐2‐ene‐1‐ol as a model substrate under optimized reaction conditions. p ‐Substituted aryl sulfonamides bearing electron‐rich or electron‐deficient substituents, alkyl sulfonamides, and heteroaryl sulfonamides undergo the amidation reaction to produce their corresponding allyl sulfonamides in good yield. Amides and anilines exhibited low activity under the optimized conditions, however, performing the reaction at 90 °C produced the target product. The scope of the allyl alcohol was investigated using p ‐toluenesulfonamide as the nucleophile and the reaction proceeded with a variety of allylic alcohols. To probe the practical utility of the H‐*BEA‐catalyzed amidation reaction, a gram‐scale reaction was performed using 1.01 g (4.8 mmol) of allyl alcohol, which afforded the target product in 88 % yield. Abstract : Towards efficient conversion of allyl alcohol into value‐added compounds: The first examples of zeolite‐catalyzed substitution of the hydroxy group in allyl alcohols with nucleophiles were developed. The zeolite‐catalyzed substitution reaction is broadly adaptable to substrates under relatively mild reaction conditions.