Selective phosphorylation of diols with a Lewis acid catalyst

Coppola, Kyle A.; Testa, Joseph W.; Allen, Emily E.; Sculimbrene, Bianca R.

doi:10.1016/j.tetlet.2014.05.047

Cited by 11 publications

(8 citation statements)

References 31 publications

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“…Along with the approach based on phosphytilation with P(III) reagents followed by oxidation, which use sensitive reagents and is limited to substrates that can tolerate an oxidative environment, several more straightforward and step- and reagent-economical phosphorylation schemes utilizing P(V) reagents (mostly phosphorochloridates) were established . However, these methods suffer from lower reactivity of phosphorus-introducing reagents and, thus, were performed with preformed alkoxides/phenolates, , or with a base, used in large excess or as a solvent and acting as a nucleophilic catalyst, a proton scavenger, or both. , Surprisingly, catalytic methods of phosphorylation with P(V) reagents, whether based on Lewis acids, or on organic nucleophiles in a catalytic amount, in conjunction with a base (which acts then as a proton scavenger only) − have been only scarcely reported, although they are presumably more efficient, more economical, and easy to handle.…”

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confidence: 99%

Phosphorylation Organocatalysts Highly Active by Design

et al. 2020

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The activity of nucleophilic organocatalysts for alcohol/phenol phosphorylation was enhanced through attaching oligoether appendages to a benzyl substituent on imidazole- or aminopyridine-based active units, presumably because of stabilizing n–cation interactions of the ethereal oxygens with the positively charged aza-heterocycle in the catalytic intermediates, and was substantially higher than that of known benchmark catalysts for a range of substrates. Density functional theory calculations and the study of analogues having a lower potential for such stabilizing interactions support our hypothesis.

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confidence: 99%

Phosphorylation Organocatalysts Highly Active by Design

et al. 2020

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“…Toward that aim, we first published the selective monophosphorylation of a variety of diols with Ti(Ot-Bu) 4 and tetrabenzyl pyrophosphate (TBPP, see Figure 1b). 23 This study highlighted that 1,3-propane diols substituted at C-2 resulted in very high yields of monophosphate product, with little to no diphosphorylation. The desymmetrization of 2-substituted-1,3-propane diols via alkylation, 24 acylation, 25 oxidation, 26 and benzoylation 27 has recently been highlighted in the literature.…”

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confidence: 80%

Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst

et al. 2021

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The desymmetrization of ten prochiral diols by phosphoryl transfer with a titanium-BINOLate complex is discussed. The phosphorylation of nine 1,3-propane diols is achieved in yields of 50–98%. Enantiomeric ratios as high as 92:8 are achieved with diols containing a quaternary C-2 center incorporating a protected amine. The chiral ligand, base, solvent, and stoichiometry are evaluated along with a nonlinear effect study to support an active catalyst species that is oligomeric in chiral ligand. The use of pyrophosphates as the phosphorylating agent in the desymmetrization facilitates a user-friendly method for enantioselective phosphorylation with desirable protecting groups (benzyl, o-nitrobenzyl) on the phosphate product.

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“…Synthesis of valuable phosphate (mono)esters, e. g. sugar phosphates, nucleotides,, metabolites, and prodrugs can be achieved by laborious chemical or mild enzymatic routes . The latter usually employ kinases and ATP in conjunction with a second enzyme for the recycling of the phosphate donor.…”

Section: Introductionmentioning

confidence: 99%

Evaluation of Natural and Synthetic Phosphate Donors for the Improved Enzymatic Synthesis of Phosphate Monoesters

et al. 2018

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Undesired product hydrolysis along with large amounts of waste in form of inorganic monophosphate by‐product are the main obstacles associated with the use of pyrophosphate in the phosphatase‐catalyzed synthesis of phosphate monoesters on large scale. In order to overcome both limitations, we screened a broad range of natural and synthetic organic phosphate donors with several enzymes on a broad variety of hydroxyl‐compounds. Among them, acetyl phosphate delivered stable product levels and high phospho‐transfer efficiency at the lower functional pH‐limit, which translated into excellent productivity. The protocol is generally applicable to acid phosphatases and compatible with a range of diverse substrates. Preparative‐scale transformations using acetyl phosphate synthesized from cheap starting materials yielded multiple grams of various sugar phosphates with up to 433 g L−1 h−1 space‐time yield and 75% reduction of barium phosphate waste.

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Selective phosphorylation of diols with a Lewis acid catalyst

Cited by 11 publications

References 31 publications

Phosphorylation Organocatalysts Highly Active by Design

Phosphorylation Organocatalysts Highly Active by Design

Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst

Evaluation of Natural and Synthetic Phosphate Donors for the Improved Enzymatic Synthesis of Phosphate Monoesters

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