Recent Advancements in the Utilization of s-Block Organometallic Reagents in Organic Synthesis with Sustainable Solvents

Author:

Rodríguez-Álvarez María Jesús1ORCID,Ríos-Lombardía Nicolás2ORCID,García-Garrido Sergio E.2ORCID,Concellón Carmen2ORCID,del Amo Vicente2ORCID,Capriati Vito1ORCID,García-Álvarez Joaquín2ORCID

Affiliation:

1. Dipartimento di Farmacia—Scienze del Farmaco, Università degli Studi di Bari Aldo Moro, Consorzio Interuniversitario Nazionale “Metodologie e Processi Innovativi di Sintesi” (C.I.N.M.P.I.S.), Via E. Orabona 4, I-70125 Bari, Italy

2. Laboratorio de Química Sintética Sostenible (QuimSinSos), Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica “Enrique Moles” (IUQOEM), Facultad de Química, Universidad de Oviedo, E-33071 Oviedo, Spain

Abstract

This mini-review offers a comprehensive overview of the advancements made over the last three years in utilizing highly polar s-block organometallic reagents (specifically, RLi, RNa and RMgX compounds) in organic synthesis run under bench-type reaction conditions. These conditions involve exposure to air/moisture and are carried out at room temperature, with the use of sustainable solvents as reaction media. In the examples provided, the adoption of Deep Eutectic Solvents (DESs) or even water as non-conventional and protic reaction media has not only replicated the traditional chemistry of these organometallic reagents in conventional and toxic volatile organic compounds under Schlenk-type reaction conditions (typically involving low temperatures of −78 °C to 0 °C and a protective atmosphere of N2 or Ar), but has also resulted in higher conversions and selectivities within remarkably short reaction times (measured in s/min). Furthermore, the application of the aforementioned polar organometallics under bench-type reaction conditions (at room temperature/under air) has been extended to other environmentally responsible reaction media, such as more sustainable ethereal solvents (e.g., CPME or 2-MeTHF). Notably, this innovative approach contributes to enhancing the overall sustainability of s-block-metal-mediated organic processes, thereby aligning with several key principles of Green Chemistry.

Funder

Spanish Ministerio de Ciencia e Innovación

European Union-Next Generation EU

Ministerio de Universidades y Plan de Recuperación, Transformación y Resiliencia

Universidad de Oviedo

PRIN project MENDELEEV

Ministero dell’Università e della Ricerca

University of Bari Aldo Moro

Interuniversity Consortium C.I.N.M.P.I.S.

Publisher

MDPI AG

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