Convenient and stereoselective dithiol synthesis

Eliel, Ernest L.; Rao, V. S.; Smith, Stanton Q.; Hutchins, Robert O.

doi:10.1021/jo00892a038

Cited by 48 publications

(21 citation statements)

References 2 publications

(4 reference statements)

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“…To afford the carbon analogue complex 7 , fluorene was treated with paraformaldehyde and NaOEt33 and the resulting 9,9′‐bis(hydroxymethyl)fluorene was tosylated to get 5 . Subsequent reaction with Na 2 S ⋅ 9 H 2 O and sulfur according to Eliel et al 34. yielded the spiro(1,2‐dithiolane‐4,9′‐fluorene) as a yellow solid.…”

Section: Resultsmentioning

confidence: 99%

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Goy

Bertini

Görls

et al. 2015

Chemistry A European J

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To learn from Nature how to create an efficient hydrogen-producing catalyst, much attention has been paid to the investigation of structural and functional biomimics of the active site of [FeFe]-hydrogenase. To understand their catalytic activities, the μ-S atoms of the dithiolate bridge have been considered as possible basic sites during the catalytic processes. For this reason, a series of [FeFe]-H2 ase mimics have been synthesized and characterized. Different [FeFe]-hydrogenase model complexes containing bulky Si-heteroaromatic systems or fluorene directly attached to the dithiolate moiety as well as their mono-PPh3 -substituted derivatives have been prepared and investigated in detail by spectroscopic, electrochemical, X-ray diffraction, and computational methods. The assembly of the herein reported series of complexes shows that the μ-S atoms can be a favored basic site in the catalytic process. Small changes in the (hetero)-aromatic system of the dithiolate moiety are responsible for large differences in their structures. This was elucidated in detail by DFT calculations, which were consistent with the experimental results.

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Section: Resultsmentioning

confidence: 99%

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Goy

Bertini

Görls

et al. 2015

Chemistry A European J

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“…tert ‐Butyl‐substituted oxygenated 1,3‐dithiane derivatives were prepared by essentially identical routes, with the parent dithiane 21 obtained by published protocols 21,22a,30. Oxidation with sodium periodate again led to the formation of the equatorial sulfoxide 23 (77 %), whereas sulfone 24 was accessed in quantitative yield by the oxidation of sulfoxide 23 with permanganate.…”

Section: Resultsmentioning

confidence: 99%

“…5‐ tert ‐Butyl‐1,3‐dithiane (21): tert ‐Butyldithiane 21 was prepared according to a published protocol 21,22a,30 . 1 H NMR (600 MHz, CDCl 3 ): δ = 0.93 (s, 9 H, t Bu), 1.73 (dtt, J = 11.3, J = 2.4, J = 1.0, 1 J C,H = 131.1 Hz, 1 H, 5‐H ax ), 2.61 (ddd, J = 13.8, J = 11.3, J = 1.0, 1 J C,H = 137.2 Hz, 1 H, 4‐H ax , 6‐H ax ), 2.82–2.85 (m, 1 J C,H ≈ 134 Hz, 2 H, 4‐H eq , 6‐H eq ), 3.35 (dt, J = 13.8, J = 1.8, 1 J C,H = 144.9 Hz, 1 H, 2‐H eq ), 4.00 (d, J = 13.8, 1 J C,H = 154.3 Hz, 1 H, 2‐H ax ) ppm.…”

Section: Methodsmentioning

confidence: 99%

Conformationally Constrained Oxides of 1,3‐Dithiane: Synthesis and NMR Spectroscopic Investigations

et al. 2012

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Conformationally constrained derivatives of 1,3‐dithianes (5‐tert‐butyl‐ and 4,6‐dimethyl‐1,3‐dithiane and dithiadecalin) have been oxidised with various oxidants to yield axial and equatorial sulfoxides, disulfoxides and sulfones. Axial sulfoxides were prepared by nucleophilic hydroxide addition to the corresponding 2‐alkylidene derivatives with subsequent retro‐aldol‐type elimination. The reaction outcome is related to the relative energies of the derivatives, as demontstrated by DFT calculations. The NMR spectroscopic data of the compounds obtained were analysed to identify 4J couplings. It was found that only 4J W couplings can be observed regardless of whether there is an axial or an equatorial sulfoxide, sulfide or sulfone group present in between the respective C–H moieties. A previously postulated γ‐gauche effect of axial sulfoxides (but not of equatorial sulfoxides or sulfones) leading to the shielding of carbon atoms is not unambiguously supported by the NMR spectroscopic data of conformationally fixed derivatives.

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“…The reaction of the disulfide anion with the atomic sulfur from the episulfide would form the trisulfide anion 4 that decomposes eliminating diatomic sulfur S 2 and generating thiolate 5 , which is a powerful nucleophile . Thus, a catalytic cycle of capture–release of sulfur is established, similar to the noncatalyzed reaction.…”

Section: Mechanismmentioning

confidence: 99%

Kinetics and mechanisms in flow systems: reduction of SO₂ on carbons

Humeres

Moreira

2012

J of Physical Organic Chem

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Surface‐science studies of some reactions have allowed postulating the mechanisms using a variety of techniques. The surface chemistry of Group IV elements has been particularly studied recently because Si, Ge, and C are semiconductors, and the surface organic chemistry to functionalize these elements has seen immense progress in recent years. In this review article we describe the methodology used to study the mechanism of a solid–gas reaction, the reduction of SO2 on carbons, and the necessary conditions that allowed the measurement of the solid conversion and product distribution when the kinetics was chemically controlled and the reaction had reached the steady state. The reaction was first‐order with respect to SO2 and with respect to carbon and the stoichiometry was determined from the product distribution. The reaction proceeds through two thermally stable reaction intermediates bound to the surface, a six‐membered ring 1,3,2‐dioxathiolane and a five‐membered ring 1,2‐oxathietene 2‐oxide or γ‐sultine, both species being in equilibrium. The reaction was shown to be reversible. The primary product is an episulfide that, after a series of consecutive reactions of atomic sulfur, is able to free sulfur. The reactivity of the intermediates and the episulfide was studied for several reactions and consistent mechanisms were postulated from the X‐ray photoelectron spectroscopy and solid state nuclear magnetic resonance spectra. Aminolysis and the reaction with alkyl halides resulted on the insertion of the alkyl moiety in the episulfide primary product, while the thiolysis and photolytic alcoholysis resulted in the insertion of the alkyl moiety in the oxidized intermediates. Copyright © 2012 John Wiley & Sons, Ltd.

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Convenient and stereoselective dithiol synthesis

Cited by 48 publications

References 2 publications

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Conformationally Constrained Oxides of 1,3‐Dithiane: Synthesis and NMR Spectroscopic Investigations

Kinetics and mechanisms in flow systems: reduction of SO₂ on carbons

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Convenient and stereoselective dithiol synthesis

Cited by 48 publications

References 2 publications

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Conformationally Constrained Oxides of 1,3‐Dithiane: Synthesis and NMR Spectroscopic Investigations

Kinetics and mechanisms in flow systems: reduction of SO2 on carbons

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Kinetics and mechanisms in flow systems: reduction of SO₂ on carbons