This article describes the synthesis of a new bio-based organocatalytic surfactant. The nine steps of the synthesis were optimized, fully respecting the principles of green chemistry. The surfactant aspect was then evaluated with the use of tensiometric studies. The molecular organization of the surfactant in vesicles in an aqueous medium was characterized by Dynamic Light Scattering (DLS) and confirmed using Density Functional Theory (DFT) modelling.
2‐MeTHF (2‐methyltetrahydrofuran) promotes the zincate‐mediated remote functionalisation of p‐iodobenzyl derivatives through metallotropy with a broad scope. This biosourced solvent remarkably impacted all the key elementary steps involved in the tandem reaction. The method tolerates a wide range of sensitive functionalities within the substrates as well as enolisable and activated or deactivated aromatic aldehydes as reaction partners. A challenging benzyl naphthalene derivative was even reacted through an original dearomatisation/rearomatisation/metallotropy chain.
The front cover picture illustrates the 1,5‐rearrangement of lithium benzyl(dibutyl)zincate derived from p‐iodobenzyl mesylate. This key elementary step is integral to a complex reaction sequence allowing the remote functionalisation of such a derivative with a wide range of aldehydes (see fruits in the tree). As a remote leaving group (here OMs) is required to trigger the chemical event, the release of LiOMs can be seen as a driving force (LiOMs is thus the driver of the boat). Details can be found in the Research Article by Alexandre Vasseur and co‐workers (A. Pierret, C. Denhez, P. C. Gros, A. Vasseur, Adv. Synth. Catal. 2022, 364, 3805–3816; DOI: 10.1002/adsc.202200475).
Lithium trialkylzincate-mediated I/Zn exchange reaction has been revisited computationally through a micro-solvation approach. A never yet investigated iodoaryl derivative bearing a potential bulky para-directing group, namely 4-iodobenzyl mesylate, was considered as a substrate. THF as typical solvent and Et3ZnLi have also been considered for the first time in such a reaction. Four mechanistic pathways have been calculated, including a literature-inspired pathway with preservation of the synergic character of the reagent (pathway 1), an OMs-directed I/Zn exchange pathway (pathway 2), a THF-solvated open complex-promoted pathway (pathway 3) and an anionic pathway (pathway 4). While pathway 4 could be fully precluded, pathway 3 turned out to be the most energetically favoured. Equivalent thermodynamic profiles were found for both pathways 1 and 2, albeit a slight preference can be attributed to the latter through micro-solvation approach. The I/Zn exchange was shown to proceed through a lithium-assisted aryl shuttle-like process. The iodoaryl substrate is first converted into ArLi intermediate which in turns reacts with the remaining diorganozinc reagent.
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