Synthesis of New Lipid‐Inspired Ionic Liquids by Thiol‐ene Chemistry: Profound Solvent Effect on Reaction Pathway

Abstract

The synthesis of a series of new lipid-inspired ionic liquids through thiol-ene "click" reaction with a single-step process. This synthesis offers considerable promise as an efficient and orthogonal method to construct structurally diverse imidazolium-type ionic liquids with linear and branched cationic tails, as well as versatility in the placement of the sulfur heteroatom. Profound solvent effect in this ene reaction regioselectivity has been observed.

Recent advances in sulfur- and phosphorous-centered radical reactions for the formation of S–C and P–C bonds

“…46 The reaction of ionic liquid alkene The Shi group explored the reactions of terminally substituted methylenecyclopropanes (MCPs) 24 with sulfenyl radicals which were generated from thiols or disulfides. In the absence of metal catalysts and radical initiators, reactions of thiols with MCPs produced Markovnikov adducts 25 as the major products along with cyclopropyl ring-opened products 26 (Scheme 16).…”

Robust design of optimal solvents for chemical reactions—A combined experimental and computational strategy

“…It has been proven that the variation of solvent can dramatically change the reaction rate (Huang and Wayner, 1994; Persson et al, 1996;Yorimitsu et al, 2000;Stanescu and Achenie, 2006) and sometimes even the reaction pathway (Yamashita et al, 2013;Mirjafari et al, 2014;Zhao et al, 2003). Therefore, the selection of an appropriate solvent is of great significance on developing high-efficiency reactive processes.…”

Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins

“…In 2014, Mirjafari and coworkers reported an interesting single step synthesis of several new lipids inspired ionic liquids 118 or 118 ′ with thiol 119 or olefin 119 ′ via thiol‐ene reaction. This protocol promised an efficient and orthogonal method for the construction of structurally different imidazolium‐type ionic liquids with linear 120 or 120 ′ and branched 121 or 121 ′ cationic tails as well as flexibility in the placement of the sulfur atom at different positions of their lipid tails (Scheme ) . In this protocol, the regioselectivity of the product is affected by the use of solvent.…”