The Use of Copper and Vanadium Mineral Ores in Catalyzed Mechanochemical Carbon–Carbon Bond Formations

Abstract

Under mechanochemical conditions in ball mills, copper-and vanadium-containing minerals initiate atom transfer radical cyclizations and oxidative couplings, respectively. Only catalytic quantities of the minerals are required, and the reactions proceed either under neat conditions or in the presence of a minimal amount of solvent.

Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry

“…These reactions were carried out in the presence of a copper sulfide mineral (covellite) and a vanadium-containing mineral (vanadinite), thus avoiding the need for the processing of the raw minerals into expensive metal catalysts (Scheme 9b). [165] Complementarily, hydrotalcite or hydroxyapatite minerals have also been used as replacement for classic bases in ball milling experiments. [167] One interesting example of how mechanochemistry complies with GC 8 can be found in the synthesis of alkoxysilanes (Scheme 10).…”

“…Most of these metal salts are obtained after extensive processing of minerals, whereby contributing to the generation of additional waste. Recently, however, ball milling techniques were applied to enable the direct use of mineral ores as catalysts in organic mechanochemistry, [165] and in prebiotic mechanochemistry [166] . For example, this concept was illustrated with the development of two mechanochemical carbon−carbon bond formation reactions: A copper‐catalyzed atom transfer radical cyclization (ATRC) and a vanadium‐catalyzed oxidative coupling.…”

“…For example, this concept was illustrated with the development of two mechanochemical carbon−carbon bond formation reactions: A copper‐catalyzed atom transfer radical cyclization (ATRC) and a vanadium‐catalyzed oxidative coupling. These reactions were carried out in the presence of a copper sulfide mineral (covellite) and a vanadium‐containing mineral (vanadinite), thus avoiding the need for the processing of the raw minerals into expensive metal catalysts (Scheme 9b) [165] . Complementarily, hydrotalcite or hydroxyapatite minerals have also been used as replacement for classic bases in ball milling experiments [167]…”

Mineral-mediated carbohydrate synthesis by mechanical forces in a primordial geochemical setting

“…In addition to possibly introducing organic matter, impact events also lead to a mechanical energy input and under these conditions the synthesis of amino acid derivatives as well as the stability of glycolaldehyde have been shown 24,25 . For laboratory purposes ball milling is the standard procedure for performing mechanochemical reactions 26 , which have been applied to mineral catalysis and even gaseous reactants [27][28][29] . Here we describe the broad applicability for the mechanochemical sugar synthesis and assess the prebiotic viability of the reaction under diverse mineral and atmospheric conditions.…”

Copper‐Containing Mineral Mediated Glaser Coupling of Terminal Alkynes

“…[30] Apart from these examples, Bolm showcased the catalytic applicability of covellite (CuS) in the preparation of six five-membered cyclic amides in Kharasch reaction. [31] In this study, we wish to present the copper mineralassisted Glaser coupling reaction of terminal alkynes. After optimization, three optimal conditions were determined utilizing both chalcocite and bornite catalysts.…”