Oxidation of Amino Diols Mediated by Homogeneous and Heterogeneous TEMPO

Testa, Maria Luisa; Ciriminna, Rosaria; Hajji, Chakib; Zaballos-García, Elena; Ciclosi, Marco; Arques, J. Sepulveda; Pagliaro, Mario

doi:10.1002/adsc.200303239

Cited by 43 publications

(21 citation statements)

References 22 publications

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“…>95:5). Deprotection of the MOM group followed by chemoselective oxidation of the primary alcohol to the acid [39][40][41] in the presence of the secondary alcohol afforded hydroxyphthioceranic acid 10, the target natural product, in 90% isolated yield (Fig. 5).…”

Section: Resultsmentioning

confidence: 98%

Synthesis of hydroxyphthioceranic acid using a traceless lithiation–borylation–protodeboronation strategy

Rasappan¹,

Aggarwal²

2014

Nature Chem

101

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In planning organic syntheses, disconnections are most often made adjacent to functional groups, which assist in C-C bond formation. For molecules devoid of obvious functional groups this approach presents a problem, and so functionalities must be installed temporarily and then removed. Here we present a traceless strategy for organic synthesis that uses a boronic ester as such a group in a one-pot lithiation-borylation-protodeboronation sequence. To realize this strategy, we developed a methodology for the protodeboronation of alkyl pinacol boronic esters that involves the formation of a boronate complex with a nucleophile followed by oxidation with Mn(OAc)3 in the presence of the hydrogen-atom donor 4-tert-butylcatechol. Iterative lithiation-borylation-protodeboronation allows the coupling of smaller fragments to build-up long alkyl chains. We employed this strategy in the synthesis of hydroxyphthioceranic acid, a key component of the cell-wall lipid of the virulent Mycobacterium tuberculosis, in just 14 steps (longest linear sequence) with full stereocontrol.

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Section: Resultsmentioning

confidence: 98%

Synthesis of hydroxyphthioceranic acid using a traceless lithiation–borylation–protodeboronation strategy

Rasappan¹,

Aggarwal²

2014

Nature Chem

101

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“…This compound was obtained by generating 4-nitrobenzoic acid cyclocondensed with unchanged (1S,2S)-ANP in the reaction system. The conversion of (1R,2R)-ANP to (1R,2R)-α-amino-β-hydroxy acid (36) by oxidation of the primary hydroxyl group mediated by homogeneous and heterogeneous 2,2,6,6-tetramethyl piperidine 1-oxyl radical (TEMPO) was reported by Pagliaroa [60]. Studies showed that heterogeneous TEMPO (the hybrid organic-inorganic silica sol-gel catalysts) is a selective mediator of the oxidation of benzylic amino diols.…”

Section: Applications In Oxidation Reactionsmentioning

confidence: 97%

An Overview of Highly Optically Pure Chloramphenicol Bases: Applications and Modifications

Yang

Fang²,

Gong³

et al. 2009

MRMC

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“…The use of the homogeneous catalyst resulted in the unselective degradation of the targeted acids, thereby showing an additional benefit of the immobilization strategy. [102] Silica-supported TEMPO was used in transition-metal-free aerobic oxidation reactions of alcohols, [53] and the electrochemical regeneration of silica-immobilized TEMPO was also reported to be feasible. [83c] Two different silica-supported TEMPO systems have been used industrially and were introduced under the trade names SilicaCat TEMPO [103] and FibreCat TEMPO.…”

Section: Immobilized Nitroxides As Reusable Catalysts In Oxidationsmentioning

confidence: 99%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

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Oxidation of Amino Diols Mediated by Homogeneous and Heterogeneous TEMPO

Cited by 43 publications

References 22 publications

Synthesis of hydroxyphthioceranic acid using a traceless lithiation–borylation–protodeboronation strategy

Synthesis of hydroxyphthioceranic acid using a traceless lithiation–borylation–protodeboronation strategy

An Overview of Highly Optically Pure Chloramphenicol Bases: Applications and Modifications

Nitroxides: Applications in Synthesis and in Polymer Chemistry

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