Redox Switching in Ethenyl‐Bridged Bisphospholes

Arkhypchuk, Anna I.; Mijangos, Edgar; Lomoth, Reiner; Ott, Sascha

doi:10.1002/chem.201405525

Cited by 11 publications

(8 citation statements)

References 24 publications

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“…Compounds 63d,e are both highly interesting molecules and feature a 2e − /2H + redox platform with chemically reversible oxidations of the two hydroxy groups. 50 The oxidation to the corresponding bisphosphol-3-ones changes the conjugation topology, which induces a hypsochromic shift in the UV/Vis spectra of the compounds. However, the back reduction proceeds through deprotonated forms of 63d,e as dianionic intermediates.…”

Section: Metal-coordinated Phosphanylphosphonate and Diacetylenic Ketonesmentioning

confidence: 99%

The Fascinating World of Phosphanylphosphonates: From Acetylenic Phosphaalkenes to Reductive Aldehyde Couplings

Mai¹,

Ott²

2019

Synlett

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This account highlights the versatility of phosphanylphosphonates, which can be used for the preparation of phosphorus-containing π-systems and as reagents for the reductive coupling of carbonyl compounds to alkenes. Phosphanylphosphonates with metal fragments coordinated to the P-lone pair have been known for a long time and they have been used for the synthesis of phosphaalkenes by means of the phospha-Horner–Wadsworth–Emmons reaction. With the original aim of incorporating phosphorus heteroatoms into classical all-carbon ethynylethene scaffolds, we entered the field of phosphanylphosphonates with the discovery that these compounds engage in complex cascade reactions with acetylenic ketones, forming 1,2-oxaphospholes, cumulenes, and bisphospholes. Later, we synthesized the first metal-free phosphanylphosphonate, which reacts with aldehydes to yield phosphaalkenes, but gives phospholones when diacetylenic ketones are used as substrates. In the final part of the account, we outline our discovery and the development of an unprecedented carbonyl–carbonyl cross-coupling reaction. This protocol offers a straightforward method for the synthesis of nonsymmetric 1,2-disubstituted alkenes directly from two dissimilar aldehydes.1 Combining Acetylenes with Phosphaalkenes2 Synthetic Examples of Acetylenic Phosphaalkenes3 The Phospha-Horner–Wadsworth–Emmons Approach to Phosphaalkenes3.1 Metal-Coordinated Phosphanylphosphonates3.2 Mechanism of the Phospha-Horner–Wadsworth–Emmons Reaction3.3 The First Metal-Free Phosphanylphosphonate and Its Reactivity with Aldehydes4 Reactions with Acetylenic Ketones4.1 Metal-Coordinated Phosphanylphosphonate and Monoacetylenic Ketones4.2 Metal-Coordinated Phosphanylphosphonate and Diacetylenic Ketones4.3 Metal-Free Phosphanylphosphonate and Diacetylenic Ketones5 Metal-Free Phosphanylphosphonate as a Coupling Reagent for Aldehydes6 E-Alkenes by the Reductive Coupling of Two Aldehydes7 Conclusions and Outlook

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Section: Metal-coordinated Phosphanylphosphonate and Diacetylenic Ketonesmentioning

confidence: 99%

The Fascinating World of Phosphanylphosphonates: From Acetylenic Phosphaalkenes to Reductive Aldehyde Couplings

Mai¹,

Ott²

2019

Synlett

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“…In the oxidized state, that is, the diketo‐form 22 b , single‐crystal X‐ray analysis confirms the interrupted π‐conjugation pathway between the two subunits showing large out‐of‐plane twists between the two subunits. Electrochemical analysis of this process indicates that the oxidation/reduction is linked with a proton‐coupled electron transfer (PCET) in which the singly oxidized/reduced intermediates are not observed due to an instantaneous 2e − /2H + PCET process …”

Section: Cyclic Structures Containing Phosphorus and Other Heteroelemmentioning

confidence: 99%

“…Electrochemical analysis of this processi ndicates that the oxidation/reduction is linked with ap roton-coupled electron transfer (PCET) in which the singly oxidized/reduced intermediates are not observed due to an instantaneous2 e À / 2H + PCET process. [60] Yama nd co-workersh ave constructed at erthiophene-based light-triggered switch with an annulated phosphole moiety 23 ( Figure 5), which undergoes photocyclization through UV irradiation (334 nm) to reach photo stationarys tates (PSS) with conversionsb etween 37 %a nd 69 %. Upon cyclization the absorptions hifts from the UV into the visible with maxima around6 00 nm concomitantly with al oss of emission.…”

Section: Molecular Switchesmentioning

confidence: 99%

Organophosphorus Compounds in Organic Electronics

Shameem

Orthaber

2016

Chemistry A European J

208

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This Minireview describes recent advances of organophosphorus compounds as opto-electronic materials in the field of organic electronics. The progress of (hetero-) phospholes, unsaturated phosphanes, and trivalent and pentavalent phosphanes since 2010 is covered. The described applications of organophosphorus materials range from single molecule sensors, field effect transistors, organic light emitting diodes, to polymeric materials for organic photovoltaic applications.

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“…Recently, we have reported a method for the preparation of persubstituted 1,2-oxaphospholes and ethylene-bridged bisphospholes starting from readily available diynones and tungsten-coordinated phosphanyl phosphonates. , This approach allowed the preparation of the target compounds in one step and in moderate to high yields. The final compounds showed interesting optoelectrochemical properties and can be used as electrochromic switches . Unfortunately, all attempts to remove the tungsten protecting groups from the P-centers to allow the use of doping strategies on these complexes were unsuccessful, outlining the necessity of developing tungsten-free approaches.…”

Section: Introductionmentioning

confidence: 99%

Phospholones from Diacetylenic Ketones: Synthesis, Properties, and Reactivity

Obermeier

Arkhypchuk

2019

J. Org. Chem.

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The reactivity of phosphanyl phosphonates toward diacetylenic ketones was studied. Reactions resulted in the selective formation of phospholones via phosphaalkene intermediates. Phospholones were obtained in yields of 37–96% depending on the substituent on the acetylenic unit. Reduction of the phenyl-substituted phospholone resulted in the formation of a persubstituted phosphole bearing a hydroxyl group in position 3 in 64% yield, and its oxidation led to oxaphospholone in 77% yield. Both of these modifications led to substantial changes in the optoelectronic properties of the compounds and bathochromic shifts of the longest wavelength absorption maximum.

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Redox Switching in Ethenyl‐Bridged Bisphospholes

Cited by 11 publications

References 24 publications

The Fascinating World of Phosphanylphosphonates: From Acetylenic Phosphaalkenes to Reductive Aldehyde Couplings

The Fascinating World of Phosphanylphosphonates: From Acetylenic Phosphaalkenes to Reductive Aldehyde Couplings

Organophosphorus Compounds in Organic Electronics

Phospholones from Diacetylenic Ketones: Synthesis, Properties, and Reactivity

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