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H‐*BEA Zeolite‐Catalyzed Nucleophilic Substitution in Allyl Alcohols Using Sulfonamides, Amides, and Anilines
Author(s) -
Ohtsuki Akimichi,
Aoki Shunsuke,
Nishida Ryo,
Morita Sachiko,
Fujii Takeshi,
Okumura Kazu
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202000296
Subject(s) - chemistry , nucleophile , yield (engineering) , allylic rearrangement , nucleophilic substitution , catalysis , medicinal chemistry , aryl , alcohol , allyl alcohol , organic chemistry , alkyl , substitution reaction , materials science , metallurgy
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/Al 2 = 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.