ARPYPHOS Ligands for Anti-Markovnikov Alkyne Hydration

Hintermann, Lukas

doi:10.1002/047084289x.rn01961

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“…Under the forcing microwave reaction conditions in aqueous methanol, ionization is brought about without an added reagent, and catalytic activity towards Markovnikov product 5 revealed, even if the conversion is low ( Table 1 , entry 1). A cyclopentadienylruthenium(II) catalyst with the ambifunctional steering ligand ISIPHOS (2-(diphenylphosphino)-6-(2,4,6-triisopropylphenyl)pyridine) [ 24 – 26 28 ] expectedly brings about anti-Markovnikov hydration, with aldehyde 6 as major product. Table 1 , entry 3 represents a first test of tungsten complex 1 in the microwave hydration protocol, at a fairly high catalyst loading of 20 mol %.…”

Section: Resultsmentioning

confidence: 99%

Is the tungsten(IV) complex (NEt₄)₂[WO(mnt)₂] a functional analogue of acetylene hydratase?

Schreyer¹,

Hintermann²

2017

Beilstein J. Org. Chem.

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The tungsten(IV) complex (Et4N)2[W(O)(mnt)2] (1; mnt = maleonitriledithiolate) was proposed (Sarkar et al., J. Am. Chem. Soc. 1997, 119, 4315) to be a functional analogue of the active center of the enzyme acetylene hydratase from Pelobacter acetylenicus, which hydrates acetylene (ethyne; 2) to acetaldehyde (ethanal; 3). In the absence of a satisfactory mechanistic proposal for the hydration reaction, we considered the possibility of a metal–vinylidene type activation mode, as it is well established for ruthenium-based alkyne hydration catalysts with anti-Markovnikov regioselectivity. To validate the hypothesis, the regioselectivity of tungsten-catalyzed alkyne hydration of a terminal, higher alkyne had to be determined. However, complex 1 was not a competent catalyst for the hydration of 1-octyne under the conditions tested. Furthermore, we could not observe the earlier reported hydration activity of complex 1 towards acetylene. A critical assessment of, and a possible explanation for the earlier reported results are offered. The title question is answered with "no".

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Section: Resultsmentioning

confidence: 99%

Is the tungsten(IV) complex (NEt₄)₂[WO(mnt)₂] a functional analogue of acetylene hydratase?

Schreyer¹,

Hintermann²

2017

Beilstein J. Org. Chem.

Self Cite

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ARPYPHOS Ligands for Anti-Markovnikov Alkyne Hydration

Cited by 1 publication

References 15 publications

Is the tungsten(IV) complex (NEt₄)₂[WO(mnt)₂] a functional analogue of acetylene hydratase?

Is the tungsten(IV) complex (NEt₄)₂[WO(mnt)₂] a functional analogue of acetylene hydratase?

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ARPYPHOS Ligands for Anti-Markovnikov Alkyne Hydration

Cited by 1 publication

References 15 publications

Is the tungsten(IV) complex (NEt4)2[WO(mnt)2] a functional analogue of acetylene hydratase?

Is the tungsten(IV) complex (NEt4)2[WO(mnt)2] a functional analogue of acetylene hydratase?

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Is the tungsten(IV) complex (NEt₄)₂[WO(mnt)₂] a functional analogue of acetylene hydratase?

Is the tungsten(IV) complex (NEt₄)₂[WO(mnt)₂] a functional analogue of acetylene hydratase?