Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds

Abstract

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Nickel‐Catalyzed Asymmetric Hydrogenation of 2‐Amidoacrylates

“…Compared to the noble transition metals, the first‐row earth‐abundant transition metals, including Mn, Fe, Co, Ni, and Cu have also shown practicable efficiency in asymmetric (transfer) hydrogenation with the benefits of lower cost and comparatively lower toxicity, thus providing a more sustainable prospect for the industrial synthesis of chiral compounds . However, until now, only cobalt complexes have afforded excellent results with regards to the asymmetric hydrogenation of 2‐amidoacrylates or 2‐amidoacrylamides for the synthesis of chiral α‐amino acids or amides (Figure ) –. However, other earth‐abundant transition metals have their own coordination modes and cannot utilize the amido‐assisted activation strategy, and this intrinsically low activity has hindered the attempts to apply them in asymmetric hydrogenation of 2‐amidoacrylates.…”

A Structurally Characterized Cobalt(I) σ‐Alkane Complex

“…In FC 6 H 5 solution, [Co( L1 )‐NBD][BAr F 4 ] reacts quantitatively with H 2 to form (in 90 % isolated yield) the brown, crystallographically characterized arene adduct [Co( L1 )(η‐FC 6 H 5 )][BAr F 4 ], with the concomitant formation of norbornane. This result shows that these cationic Co I systems will promote the hydrogenation of alkenes, similar to the DuPhos variants . For [Co( L2 )‐NBD][BAr F 4 ], hydrogenation in FC 6 H 5 solution results in decomposition to a mixture of products.…”

“…This starts from CoCl 2 , involves a KC 8 reduction, a CH 2 Cl 2 extraction, and delivers, respectively, lilac and green crystalline products in moderate yield . Our method complements that recently reported by Chirik using DuPhos‐based ligands . [Co( L1 )(arene)][BF 4 ] complexes are also known .…”

“…[21] Our method complements that recently reported by Chirik using DuPhos-based ligands. [22] [Co(L1)-(arene)][BF 4 ] complexes are also known. [23] The solid-state structure of [Co(L2)-NBD][BAr F 4 ] is shown in Figure 2, with that for [Co(L1)-NBD][BAr F 4 ] given in the Supporting Information.…”

Mukaiyama‐Preis: M. D. Burke und S. Matsunaga / Ryoji‐Noyori‐Preis und Paracelsus‐Preis: S. E. Denmark / Henry J. Albert‐Preis: M. P. Doyle / ORCS‐Preise: P. Chirik und J. J. Spivey / FNP‐Preis: M. Drąg

“…Dabei geht es um Erkenntnisse zur elektronischen Struktur, die Kontrolle des Redoxverhaltens und um neue industrielle Transformationen für Kohlenwasserstoffe, Pharmazeutika sowie Geruchs‐ und Geschmacksstoffe. In einer Angewandte‐Chemie ‐Zuschrift berichtete Chirik unlängst über kationische Bis(phosphan)cobalt‐Diene und ‐Arene für katalytische Hydrierungen …”