Catalytic Carbonylative Rearrangement of Norbornadiene via Dinuclear Carbon–Carbon Oxidative Addition

Abstract

Single bonds between carbon atoms are inherently challenging to activate using transition metals; however, ring-strain release can provide the necessary thermodynamic driving force to make such processes favorable. In this report, we describe a strain-induced C-C oxidative addition of norbornadiene. The reaction is mediated by a dinuclear Ni complex, which also serves as a catalyst for the carbonylative rearrangement of norbornadiene to form a bicyclo[3.3.0] product.

The Importance of Ligand‐Induced Backdonation in the Stabilization of Square Planar d10 Nickel π‐Complexes

“…For example, we are exploring the organometallicc hemistry of nickel, [10][11][12][13][14] which has undergone ar enaissance in recent years. [15][16][17][18][19][20][21] Our focus has been the structure and reactivityo fn ickel p-complexes, which have been reported in aw ide range of catalytic processes, including the coupling of CO 2 and ethylene, [5,[22][23][24][25][26][27][28][29][30][31][32] intermolecular Tischenkoc oupling, [33][34][35] benzoxasilole synthesis, [36,37] the aldol reaction, [38] allylic alkylation, [39] allylic amination, [40] allylic amidation, [41] epoxide functionalization, [42] and Suzuki-Miyaura coupling. [43] Nickel p-complexes of heteroarenes have also been identified as key intermediates in nickel-catalysed catalystt ransfer polycondensation to form polythiophenes.…”

“…We have recently become interested in exploring the fundamental organometallic chemistry of earth‐abundant, first‐row transition metals. For example, we are exploring the organometallic chemistry of nickel, which has undergone a renaissance in recent years . Our focus has been the structure and reactivity of nickel π‐complexes, which have been reported in a wide range of catalytic processes, including the coupling of CO 2 and ethylene, intermolecular Tischenko coupling, benzoxasilole synthesis, the aldol reaction, allylic alkylation, allylic amination, allylic amidation, epoxide functionalization, and Suzuki–Miyaura coupling .…”

Cyclophanes as Platforms for Reactive Multimetallic Complexes

“…6–10 Indeed, such cooperativity is readily apparent in synthetic dimetallic catalysts that effect oxidative addition or reductive elimination in which both metal ions undergo a change in their formal oxidation number. 11–13 As highlighted recently, multiple metal sites in a catalyst can improve conversion values ( e.g., number of turnovers) and product selectivity. 14,15 Analogous trends are also observed for higher nuclearity compounds, supporting a multinuclear hypothesis for multi-electron redox processes.…”

The importance of ligand-induced backdonation in the stabilization of square planar d10 nickel π-complexes

“…For example, we are exploring the organometallic chemistry of nickel, [10][11][12][13][14] which has undergone a renaissance in recent years. [15][16][17][18][19][20][21] Our focus has been the structure and reactivity of nickel π-complexes, which have been reported in a wide range of catalytic processes, including the coupling of CO 2 and ethylene, [5,[22][23][24][25][26][27][28][29][30][31][32] intermolecular Tischenko coupling, [33][34][35] benzoxasilole synthesis, [36,37] the aldol reaction, [38] allylic alkylation, [39] allylic amination, [40] allylic amidation, [41] epoxide functionalization, [42] and Suzuki-Miyaura coupling. [43] Nickel πcomplexes of heteroarenes have also been identified as key intermediates in nickel-catalysed catalyst transfer polycondensation to form polythiophenes.…”