Mechanochemical Activation of Iron Cyano Complexes: A Prebiotic Impact Scenario for the Synthesis of α‐Amino Acid Derivatives

Abstract

Mechanochemical activation of iron cyano complexes by ball milling results in the formation of HCN, which can be trapped and incorporated into α-aminonitriles. This prebiotic impact scenario can be extended by mechanochemically transforming the resulting α-aminonitriles into α-amino amides using a chemical route related to early Earth conditions.

Mechanochemical Palladium‐Catalyzed Carbonylative Reactions Using Mo(CO)6

“…In the case of mechanochemical reactions involving gaseous components, gases such as H 2 , O 2 , CO, CO 2 , HCN, C 3 H 6 , CH 4 , among others, have been reported to undergo clean chemical transformations inside ball mills in various areas of synthetic chemistry. For example, in 2017 Hapiot and co‐workers reported a rhodium‐catalyzed mechanochemical hydroformylation of styrene derivatives in a planetary ball mill using a mixture of CO/H 2 (Scheme a) .…”

“…[2] Intuitively,m echanochemical activation by ball milling appearsm ore appropriate for solids amples.H owever, mechanical treatment of soft organic materials, liquidsa nd even gaseous reactants hasproven equally effective. [3] In the case of mechanochemical reactions involving gaseous components, gases such as H 2 , [4] O 2 , [5] CO, [6] CO 2 ,[7] HCN, [8] C 3 H 6 , [9] CH 4 , [10] among others, [11] have been reported to undergo clean chemical transformationsi nside ball mills in various areas of synthetic chemistry.F or example, in 2017 Hapiot and coworkers reported ar hodium-catalyzed mechanochemical hydroformylation of styrene derivatives in ap lanetary ball mill using am ixture of CO/H 2 (Scheme 1a). [12] Although the reactions led to high conversions of substrates such as 2-vinylnaphthalenew ithout the need fore xternal heating,t hey required a1 5bar pressure of carbon monoxide and hydrogen inside ap ressurized milling vessel.…”

Mechanoenzymatic Transformations in the Absence of Bulk Water: A More Natural Way of Using Enzymes

“…This observation is consistent with the ongoing change in our understanding of chemical transformations, with the growing realization that many reactions readily proceed in solvent‐less mechanochemical environments . Indeed, mechanochemistry, which was recently proposed to be involved in the emergence of small organic molecules on the early Earth, has successfully provided routes to chemical selectivity, as well as reactions or molecules that have otherwise been considered difficult or even impractical to access. Although mechanoenzymatic reactivity is in a very early stage of development, it has already sparked a significant amount of interest, and provided simple solutions to streamline industrial processing of, for example, lignocellulosic material.…”

“…It is our view that solvent-less environments found in liquidassistedg rinding and/ora ging in moist air,a re more effective than conventional dilute solutions in replicating the natural environmento fm any enzymes.M uch more akin to low h conditions of liquid-assisted mechanochemistry,e nzymes secreted by microorganisms thrive on moist surfaces, and intracellular enzymes functioni nh ighly concentrated, organized environments.T his observation is consistent with the ongoing change in our understanding of chemical transformations, [161] with the growingr ealization that many reactions readily proceed in solvent-less mechanochemicale nvironments. [18,115,[162][163][164][165][166][167][168] Indeed, mechanochemistry,w hichw as recently proposed to be involved in the emergence of small organic molecules on the early Earth, [169] has successfully provided routes to chemical selectivity, [19,170,171] as well as reactions [172,173] or molecules [174][175][176] that have otherwiseb een considered difficult or even impractical to access. Although mechanoenzymatic reactivity is in a very early stage of development, it has already sparked as ignificanta mount of interest, [177] and provided simple solutions to streamline industrial processing of, for example, lignocellulosic material.…”

Mechanochemie gasförmiger Reaktanten

“…[78] Fürdie mechanische Deformation von Ferrocenderivaten durch Ultraschallbehandlung [79] oder die plastische Deformation von Metallkomplexen, wie K 3 [Fe(CN) 6 ](III), [80,81] bei hohen Drücken wurde beobachtet, dass sie die Freisetzung von Metallionen oder eine ¾nderung des Oxidationszustands des Metallzentrums einleiten kçnnen. [82] Alle hier vorgestellten Beispiele zeigen die Kompatibilität von Kugelmahltechniken mit chemischen Umwandlungen, in denen Reaktanten in der Gasphase beteiligt sind. B. fürd ie Anwendung von Scherkräften auf Kaliumhexacyanidoferrat-(III) bekannt, dass sie die Bildung von K 4 [Fe(CN) 6 ](II) mit einhergehender Freisetzung von Dicyan (C 2 N 2 )o der HCN und HOCN,w enn Wasser anwesend ist, auslçsen.…”