A regioselective synthesis of the dephospho ditholene protected molybdopterin

Pimkov, Igor V.; Peterson, Antoinette A.; Vaccarello, David N.; Basu, Partha

doi:10.1039/c4ra02786h

Cited by 9 publications

(6 citation statements)

References 40 publications

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“…Pterin‐Mo chemistry has been a topic of interest since 1982, when the structure of MPT was proposed by Rajagopalan and co‐workers . Progress in this difficult area has been slow and hard‐won but the total syntheses of MPT and the Mo‐cofactor (Moco) are advancing . Scorpionate ligands are playing their part in the stabilization of Mo‐pterin complexes, permitting the investigation of their structures, properties and behavior.…”

Section: Stabilization and Electronic Structure Of Oxido‐mo Dithiomentioning

confidence: 99%

Scorpionate Complexes as Models for Molybdenum Enzymes

Young¹

2016

Eur J Inorg Chem

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Scorpionate ligands have supported the development of a number of important synthetic models for pterincontaining molybdenum enzymes. These ligands stabilize biologically relevant mononuclear oxido-and sulfido-Mo(VI,V,IV) complexes capable of sustaining a wide range of biomimetic reactions, including oxygen atom, sulfur atom and coupled electron-proton transfer reactions. Studies of scorpionate-Mo compounds have also provided key insights into the bonding in

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Section: Stabilization and Electronic Structure Of Oxido‐mo Dithiomentioning

confidence: 99%

Scorpionate Complexes as Models for Molybdenum Enzymes

Young¹

2016

Eur J Inorg Chem

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“…Furthermore, the synthesis of MPT represents a major chemical challenge and, although significant advances have been reported,14e,17 further work is still required. In their synthetic studies,17a–17f Joule, Garner et al used [(η 5 ‐C 5 H 5 )Co] 2+ as the metal centre, with the organic framework being bound to this through its ene‐1,2‐thiolate group 14e,17g,17h. This strategy avoided complications associated with the chemistry of [Mo IV O] 2+ , [Mo V O] 3+ and [Mo VI O 2 ] 2+ centres, including unwanted dimerization reactions.…”

Section: Introductionmentioning

confidence: 99%

Twisted Baskets

Hermann

Pratumyot

Polen

et al. 2015

Chemistry A European J

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A preparative procedure for obtaining a pair of twisted molecular baskets, each comprising a chiral framework with either right ((P)-1syn) or left ((M)-1syn) sense of twist and six ester groups at the rim has been developed and optimized. The racemic (P/M)-1syn can be obtained in three synthetic steps from accessible starting materials. The resolution of (P/M)-1syn is accomplished by its transesterification with (1R,2S,5R)-(-)-menthol in the presence of a Ti(IV) catalyst to give diastereomeric 8(P) and 8(M). It was found that dendritic-like cavitands 8(P) and 8(M), in CD2Cl2, undergo self-inclusion ((1)H NMR spectroscopy) with a menthol moiety occupying the cavity of each host. Importantly, the degree of inclusion of the menthol group was ((1)H NMR spectroscopy) found to be greater in the case of 8(P) than 8(M). Accordingly, it is suggested that different folding characteristic of 8(P) and 8(M) ought to affect the physicochemical characteristics of the hosts to permit their effective separation by column chromatography. The absolute configuration of 8(P)/8(M), encompassing right- and left-handed "cups", was determined with the exciton chirality method and also verified in silico (DFT: B3LYP/TZVP). Finally, the twisted baskets are strongly fluorescent due to three naphthalene chromophores, having a high fluorescence quantum yield within the rigid framework of 8(P)/8(M).

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“…Much of this model work first required the development of new pterin chemistry. 26, 27, 29, 53, 54 The most recent results from our laboratories are described below and placed into the context of the question “what is the role of the pyranopterin dithiolene ligand in Moco?”…”

Section: Properties That May Influence the Role Of The Pterin-dithiolmentioning

confidence: 99%

“…More recently, the synthetic approach of using the trithiolene unit to protect the core structure of a pterin-dithiolene ligand was reported by Basu 29 et al (Fig. 9).…”

Section: Models Of the Mpt Ligandmentioning

confidence: 99%

“…This biochemical work prompted the development of subsequent models incorporating dithiolene or pterin structures. 6, 20–29 Spectroscopic studies coupled with computational methods suggested that the dithiolene unit was likely playing key electronic roles in modulating the Mo redox potentials through controlling the electronic structure, and in directing substrate reaction at a specific oxo ligand. 30–33 Pterin molecules were established as potential redox partners.…”

Section: Introductionmentioning

confidence: 99%

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Recent developments in the study of molybdoenzyme models

Basu

Burgmayer

2015

J Biol Inorg Chem

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Over the past two decades a plethora of crystal structures of molybdenum enzymes has appeared in the literature providing a clearer picture of the enzymatic active sites and increasing the challenge to chemists to develop accurate models for those sites. In this minireview we discuss the most recent model studies aimed to reproduce detailed features of the pterin-dithiolene ligand, both as the uncoordinated form and as a chelate coordinated to molybdenum.

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A regioselective synthesis of the dephospho ditholene protected molybdopterin

Cited by 9 publications

References 40 publications

Scorpionate Complexes as Models for Molybdenum Enzymes

Scorpionate Complexes as Models for Molybdenum Enzymes

Twisted Baskets

Recent developments in the study of molybdoenzyme models

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