1129-74-4Relevant articles and documents
FREE RADICAL REACTIONS INITIATED BY ORGANOCOBALT COMPLEXES. A NEW METHOD FOR THE DEGRADATION OF CARBOXYLIC ACIDS TO FUNCTIONALISED NOR-ALKANES VIA ACYLCOBALT SALOPHEN INTERMEDIATES.
Patel, Vinod F.,Pattenden, Gerald
, p. 707 - 710 (1988)
Arylmethyl- and allyl-acylcobalt salophens, undergo facile C-Co bond homolysis and in situ decarbonylation, producing new (alkyl) radical centres which can be intercepted with oxygen, nitrogen, halogen, sulphur and selenium containing radical trapping agents, leading to functionalised nor-alkanes (Scheme).
Asymmetric Enzymatic Synthesis of Allylic Amines: A Sigmatropic Rearrangement Strategy
Prier, Christopher K.,Hyster, Todd K.,Farwell, Christopher C.,Huang, Audrey,Arnold, Frances H.
supporting information, p. 4711 - 4715 (2016/04/19)
Sigmatropic rearrangements, while rare in biology, offer opportunities for the efficient and selective synthesis of complex chemical motifs. A "P411" serine-ligated variant of cytochrome P450BM3 has been engineered to initiate a sulfimidation/[2,3]-sigmatropic rearrangement sequence in whole E. coli cells, a non-natural function for any enzyme, providing access to enantioenriched, protected allylic amines. Five mutations in the enzyme substantially enhance its activity toward this new function, demonstrating the evolvability of the catalyst toward challenging nitrene transfer reactions. The evolved catalyst additionally performs the highly enantioselective imidation of non-allylic sulfides.
Cobalt-mediated Reactions in Synthesis. The Degradation of Carboxylic Acids to Functionalised Noralkanes via Acylcobalt Salophen Intermediates
Patel, Vinod F.,Pattenden, Gerald,Thompson, David M.
, p. 2729 - 2734 (2007/10/02)
Arylmethyl- and allyl-carbonylcobalt salophen complexes, e.g. (7), (8), (9), and (22), readily undergo carbon-to-cobalt-bond homolysis and in situ decarbonylation, producing new alkyl radical centres which can be intercepted with oxygen-, nitrogen-, halogen-, sulphur-, and selenium-containing trapping agents leading to functionalised noralkanes.The sequence constitutes a useful, and in some cases more flexible, variant of the classical Hunsdiecker reaction, and amounts to a cobalt equivalent of the Barton radical decarboxylation reaction of carboxylic acids via their corresponding thiohydroxamic esters.In a similar manner, irradiation of the oxy-substituted acylcobalt salen reagents (25) and (26) in the presence of tetramethylpiperidine oxide produces the products (14) and (27), respectively, resulting from homolysis-decarboxylation and alkyl-radical trapping.In the absence of radical-trapping agents, irradiation of (7c) produces (18), and irradiation of (29) leads to the but-2-enolide (32).
