Nucleophilic substitution of propargyl alcohols with aliphatic alcohols, aliphatic amines and heterocycles catalyzed by 4-nitrobenzenesulfonic acid: a scalable and metal-free process

Scope and advances in the catalytic propargylic substitution reaction

“…Savarimuthu and co-workers in 2014 employed NBSA as a cost-effective catalyst for the nucleophilic substitution of propargyl alcohols 23 with several nucleophiles like alcohols, amines, and heterocycles, Scheme 200. 233 The reaction was devoid of any corrosive and costly metal catalysts, toxic solvents and does not involve any column chromatographic purication. The authors screened several protic acids like p-toluenesulfonic acid (p-TSA), benzene sulfonic acid (BSA), p-nitrobenzene sulfonic acid (NBSA) in acetonitrile, tetrahydrofuran and dichloromethane solvents.…”

“…Savarimuthu and co-workers in 2014 employed NBSA as a cost-effective catalyst for the nucleophilic substitution of propargyl alcohols 23 with several nucleophiles like alcohols, amines, and heterocycles, Scheme 200 . 233 …”

Recent Advances in Direct Catalytic Dehydrative Substitution of Alcohols

“…This catalyst system was shown to be active at room temperature and compatible with O-, N-and C-nucleophiles. 91 A similar catalytic method, also applicable to a range of O-, N-and C-nucleophiles, was reported by Sheppard and co-workers in 2012, whereby 1 mol% AgNTf 2 at room temperature facilitated conversion of propargylic alcohols into a range of functionalized products. 92 In 2015, Sanz and co-workers described a p-toluenesulfonic acid catalyzed cascade cyclization between 1,4-propargylic diols and indoles yielding benzofulvene derivatives.…”

TfOH-Promoted Reactions of TMS-Ethers of CF3–Pentenynoles with Arenes. Synthesis of CF3-Substituted Pentenynes, Indenes, and Other Carbocyclic Structures

“…Propargylic alcohols also have a wide range of applications in oxidation, ring expansion, tandem reactions, benzannulation, and Meyer-Schuster rearrangement and play a huge role in the synthesis of carbo- and heterocyclic compounds . One of the most important transformation of allylic and propargylic alcohols is their electrophilic acitvation with Brønsted and Lewis acids, including the classical Friedel–Crafts process. − …”