Electronic Effects in Olefin Oxidation by Imidoosmium(<scp>VIII</scp>) Compounds

The 1,2-diamine moiety is a ubiquitous structural motif present in a wealth of natural products, including non-proteinogenic amino acids and numerous alkaloids, as well as in pharmaceutical agents, chiral ligands and organic reagents. The biological activity associated with many of these systems and their chemical utility in general has ensured that the development of methods for their preparation is of critical importance. While a wide range of strategies for the preparation of 1,2-diamines have been established, the diamination of alkenes offers a particularly direct and efficient means of accessing these systems. The purpose of this review is to provide an overview of all methods of direct alkene diamination, metal-mediated or otherwise.

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“…This reactivity reflects the increased nucleophilicity of the imido complexes in comparison with OsO 4 . 217 …”

Section: Transition Metal-catalyzed Diaminationmentioning

confidence: 99%

Methods for direct alkene diamination, new & old

2012

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“…Intermediate 15 can be further oxidized to aryl aldehyde 22 under mild conditions [ 17 , 18 ]. Subsequent transformation of 22 via the formation of oxime and dehydration could yield 23 (80%) [ 19 , 20 ].…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Pelorol and Its Analogs and Their Inhibitory Effects on Phosphatidylinositol 3-Kinase

et al. 2016

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There are numerous biologically active substances with novel structures and unique physiological functions in marine organisms. These substances are important sources of new lead compounds. Pelorol is a natural product isolated from marine organisms that possesses a novel structure with high bioactivity. In this paper, the synthesis of pelorol has been completed, and the synthesis of some intermediates has been optimized and scaled up. Five pelorol analogs have also been prepared. Preliminary biological activity testing demonstrated that compounds 5 and 6 might be potential lead compounds for cancer therapy.

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“…A first competition experiment for oxidation of dimethyl fumarate with OsO 2 (N t Bu) 2 or OsO(N t Bu) 3 revealed a higher reaction rate for these reagents than for the related compounds OsO 4 and OsO 3 (N t Bu). 36 In fact, the relative reactivity in the oxidation of dimethyl fumarate was found to increase in the following order:…”

Section: General Aspectsmentioning

confidence: 99%

The development of asymmetric diamination of alkenes with imido-osmium reagents

Muñiz¹

2005

New J. Chem.

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Defined oxidative transformations of alkenes offer a versatile route to higher-functionalised organic entities. While processes such as dihydroxylation and aminohydroxylation have reached a remarkable level of efficiency with regard to substrate scope and enantioselection, the related process of diamination has received only scant attention. This perspective summarises recent results in the development of asymmetric diamination of alkenes employing bis-and tris(imido)osmium oxidants. Two different asymmetric courses were developed which consist of diastereoselective diamination employing chiral auxiliaries and enantioselective diamination in the presence of a chiral metal catalyst. The diamination products are obtained as monomeric diamine-ligated osmium complexes of unprecedented stability, and all results from these studies represent a completely new chapter in osmium-mediated alkene oxidation.

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Electronic Effects in Olefin Oxidation by Imidoosmium(VIII) Compounds

Cited by 34 publications

References 29 publications

Methods for direct alkene diamination, new & old

Methods for direct alkene diamination, new & old

Synthesis of Pelorol and Its Analogs and Their Inhibitory Effects on Phosphatidylinositol 3-Kinase

The development of asymmetric diamination of alkenes with imido-osmium reagents

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