Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms

Abstract

Catalytic reactions have played an indispensable role in organic chemistry for the last several decades. In particular, catalytic multicomponent reactions have attracted a lot of attention due to their efficiency and expediency towards complex molecule synthesis. The presence of bismetallic reagents (e.g. B–B, Si–Si, B–Si, Si–Sn, etc.) in this process renders the products enriched with various functional groups and multiple stereocenters. For this reason, catalytic bismetallative coupling is considered an effective method to generate the functional and stereochemical complexity of simple hydrocarbon substrates. This review highlights key developments of transition-metal catalyzed bismetallative reactions involving multiple π components. Specifically, it will highlight the scope, synthetic applications, and proposed mechanistic pathways of this process.

Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*RhIII‐Catalyzed C−H Activation

“…[5] Despite considerable efforts in this area, most of the protocols developed to date remain limited to two-component reactions.M ulticomponent reactions provide an attractive alternative to streamline the synthesis of complex organic scaffolds. [6,7] Thus,modular three-component carboamination reactions with independent carbon and nitrogen sources are highly desirable. [8] In this regard, Engle and co-workers developed an elegant protocol for the regioselective carboamination of unactivated alkenes involving various nitrogen nucleophiles and carbon Scheme 1.…”

Tertiary α‐Silyl Alcohols by Diastereoselective Coupling of 1,3‐Dienes and Acylsilanes Initiated by Enantioselective Copper‐Catalyzed Borylation

“…Harutyunyan and co-workers later substantially expanded the scope with the development of ac opper-catalyzed alkylation of aryl-and alkenyl-substituted acylsilanes with Grignard reagents as nucleophiles (Scheme 1, top). 1,3-Dienes,p articularly low-cost isoprene,are an often-employed p-system, [20] and their use in these three-component reactions currently attracts much attention. [12][13][14][15][16][17][18][19] By this method, densely functionalized boron compounds are made available with high levels of regio-and stereocontrol.…”

“…[12][13][14][15][16][17][18][19] By this method, densely functionalized boron compounds are made available with high levels of regio-and stereocontrol. 1,3-Dienes,p articularly low-cost isoprene,are an often-employed p-system, [20] and their use in these three-component reactions currently attracts much attention. [14a,15b,16c-e,18c,d,19a] Just four of these reports are enantioselective variants,n amely the beautiful work of the groups of Hoveyda, [15b] Liao, [14a] and Brown.…”

Tertiäre α‐Silylalkohole mittels diastereoselektiver Kupplung von 1,3‐Dienen und Acylsilanen, eingeleitet durch enantioselektive kupferkatalysierte Borylierung

“…Später erweiterten Harutyunyan und Mitarbeiter die Anwendungsbreite maßgeblich durch die Entwicklung einer kupferkatalysierten Alkylierung von arylund alkenylsubstituierten Acylsilanenm it Grignard-Reagenzien als Nukleophile (Schema 1, oben). 1,3-Diene,i nsbesondere kostengünstiges Isopren, sind ein häufig verwendetes p-System, [20] und ihr Einsatz in diesen Dreikomponentenreaktionen erregt momentan viel Aufmerksamkeit. [12][13][14][15][16][17][18][19] Damit werden dicht funktionalisierte Borverbindungen mit hoher Regio-und Stereokontrolle zugänglich gemacht.…”

“…[12][13][14][15][16][17][18][19] Damit werden dicht funktionalisierte Borverbindungen mit hoher Regio-und Stereokontrolle zugänglich gemacht. 1,3-Diene,i nsbesondere kostengünstiges Isopren, sind ein häufig verwendetes p-System, [20] und ihr Einsatz in diesen Dreikomponentenreaktionen erregt momentan viel Aufmerksamkeit. [14a, 15b,16c-e,18c,d, 19a] Lediglich vier dieser Beiträge,und zwar die schçnen Arbeiten der Gruppen von Hoveyda, [15b] Liao [14a] und Brown, [16d,e] [10] Wiru ntersuchten als nächstes die Anwendungsbreite an Acylsilanen (Schema 2).…”