Directed ortho-metalation–nucleophilic acyl substitution strategies in deep eutectic solvents: the organolithium base dictates the chemoselectivity

Abstract

Organolithium-mediated chemoselectivity in deep eutectic solvents: basicity vs. nucleophilicity.

Synthesis of α,ω‐Bis‐Enones by the Double Addition of Alkenyl Grignard Reagents to Diacid Weinreb Amides

“…[7b], [7c] In this context, it should be noted that the addition of aryl or alkyl Grignard and lithium reagents to bis‐Weinreb amides has been reported , . Recent studies further show that such nucleophilic acyl substitution reactions can be even carried out in protic media under air, efficiently suppressing the over‐addition in the addition of organometallic reagents to simple N , N ‐dialkylamides …”

Deep Eutectic Solvents as Effective Reaction Media for the Synthesis of 2-Hydroxyphenylbenzimidazole-Based Scaffolds en Route to Donepezil-Like Compounds

“…Because of their ability to act also as catalysts and reagents [29,30], DESs have been primarily investigated in extraction and separation processes [31][32][33][34], in material sciences [35], for metal electrodeposition [36], and for the synthesis of heterocycles [37]. Emerging and hot fields of applications are represented by organometallics [38][39][40], metal- [41][42][43][44][45][46][47][48], bio- [49][50][51][52][53], and organo-catalysis [54][55][56][57], electrochemistry [58], photosynthesis [59] and energy technology [60,61]. Building upon our interests in the synthesis of drugs and heterocycles using eco-friendly reaction media like DESs [43][44][45][46][47]55,62,63] and water [64], herein we report the sustainable preparation of several 2-hydroxyphenylbenzimidazole derivatives and the whole synthesis of PZ1 [19] in selected eutectic mixtures.…”

DESign of Sustainable One-Pot Chemoenzymatic Organic Transformations in Deep Eutectic Solvents for the Synthesis of 1,2-Disubstituted Aromatic Olefins

“…In this context and during the last decade, a new family of sustainable reaction media, the socalled Deep Eutectic Solvents (DESs) (Abbott et al, 2003(Abbott et al, , 2004 has attracted the attention of many research groups worldwide. As consequence, these neoteric solvents have been broadly applied in chemistry as sustainable reaction media for: (i) polar organometallic chemistry (Mallardo et al, 2014;Vidal et al, 2014Vidal et al, , 2016Sassone et al, 2015;García-Álvarez et al, 2018;Rodríguez-Álvarez et al, 2018;Ghinato et al, 2019); (ii) metal catalyzed organic reactions (García-Álvarez, 2015; Vidal and García-Álvarez, 2019); (iii) biocatalysis (Gotor-Fernández and Paul, 2018); (iv) traditional organic synthesis (Liu et al, 2015;Alonso et al, 2016); (v) metal extraction and electrochemistry (Smith et al, 2014;Millia et al, 2018); and (v) polymer science (Carriazo et al, 2012;del Monte et al, 2014;Mota-Morales et al, 2018;Quirós-Montes et al, 2019;Roda et al, 2019;Sánchez-Condado et al, 2019). These sustainable eutectic solvents can be obtained just by mixing (without any further steps of purification or isolation) two molecules capable of forming a complex intermolecular network based on hydrogenbond interactions.…”