Stereospecific vicinal oxyamination of olefins by alkylimidoosmium compounds

Patrick, Donald W.; Truesdale, Larry K.; Biller, Scott A.; Sharpless, K. Barry

doi:10.1021/jo00407a016

Cited by 79 publications

(27 citation statements)

References 6 publications

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“…Indeed, reaction of 2 with dimethyl fumarate (5) in the presence of TMEDA gave the expected complex 25 (Scheme 7). Since the primarily formed N-(tert-butyl)azaglycolate has been shown to be rather unstable, [11,12] isolation of 25 proves the beneficial influence of the chelating diamine in stabilising the azaglyolate osmium intermediate as already observed by Donohoe. Product 25 was isolated as an inseparable mixture of two isomers.…”

Section: Ligand Coordinationsupporting

confidence: 54%

“…However, it had already been noted by Sharpless that 2 represents a slightly softer oxidant than 1 and thus should be regarded as an electrophilic reagent with less pronounced character than 1. [11,12] This can be explained by the electron lone pair at the imido nitrogen atom which upon coordination to the metal centre diminishes the electrophilicity. Such an assumption is strengthened by X-ray analyses which show a linear imido ligand with a formal 4e count.…”

Section: Hammett Correlationsmentioning

confidence: 99%

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Electronic Effects in Olefin Oxidation by Imidoosmium(VIII) Compounds

Muñiz

2004

Eur J Org Chem

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Imido osmium(VIII) complexes are versatile oxidants for C−C double bond functionalisation. Despite their structural similarity with OsO4 their reactivity cannot always be compared with this seminal reagent. Detailed investigations including kinetic competition experiments are presented that uncover the electronic and steric preferences of osmium imido complexes. The different behaviour of OsO4 and its imido derivatives towards tertiary amines and diamines is clarified. Hammett correlation studies reveal that the reactivity spectrum of the respective oxidants ranges from a strongly electrophilic behaviour in the case of OsO4 to a rather nucleophilic character as encountered for OsO(NtBu)3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Ligand Coordinationsupporting

confidence: 54%

Section: Hammett Correlationsmentioning

confidence: 99%

Electronic Effects in Olefin Oxidation by Imidoosmium(VIII) Compounds

Muñiz

2004

Eur J Org Chem

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“…[187] The use of OsO 3 (NR) compounds in amino-hydroxylation of alkenes was pioneered by Sharpless. [188][189][190] As is …”

Section: J F Berrymentioning

confidence: 99%

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Berry

2009

Comments on Inorganic Chemistry

285

232

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Compounds that contain a late transition metal-nitrogen multiple bond represent important reactive intermediate species in many useful organic and inorganic transformations. In order to understand the role that these intermediates play in reactions, it is important to have a full understanding of their electronic structure. This paper reviews the known structural motifs that occur in late transition metal nitrido and imido compounds, and provides a correlation between geometric structure and electronic structure. Also, intermediate species that have been postulated but not yet isolated are discussed, as these compounds represent exciting targets for further efforts in synthetic inorganic chemistry.

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“…This is evident from the 1 H NMR spectrum, which shows a doublet at δ ϭ 4.65 (3d) and 4.60 (3e) with coupling constants 3 J ϭ 3.4 Hz characteristic for a cis stereochemistry. [17] Our results demonstrate that the six-membered transition state is more favorable than the seven-membered one even when an OMe Scheme 5. 7-X-TetralPY2 ligands 1d,e in oxygen atom transfer reaction substituent activates the γ benzylic position (Scheme 5).…”

Section: Ligandsmentioning

confidence: 65%