Organic Selenocyanates, Tellurocyanates and Related Compounds

Toshimitsu, Akio

doi:10.1002/9780470682531.pat0723

Cited by 3 publications

(3 citation statements)

References 195 publications

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“…Both challenges could be addressed in principle by selecting reactions amenable to fast and easy workup. Of the many methods currently available for the synthesis of 1-alkaneselenols and their precursors, − we selected the route illustrated in Scheme , as exemplified by the synthesis of 1-octaneselenol ( 4a ).…”

Section: Introductionmentioning

confidence: 99%

A Scalable Process for the Synthesis of 1,2-Dialkyldiselanes and 1-Alkaneselenols

Cooksey

Kocieński

Blacker

2019

Org. Process Res. Dev.

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A four-step telescoped process for the synthesis of 1-alkaneselenols entails (1) the rapid formation of potassium selenocyanate from potassium cyanide and selenium in methanol, (2) the nucleophilic substitution of bromoalkanes or alkyl tosylates with potassium selenocyanate, (3) the mild base-catalyzed conversion of the resultant 1-alkaneselenocyanates to 1,2dialkyldiselanes (the Krief reaction), and (4) the reduction of the resultant 1,2-dialkyldiselanes with hypophosphorous acid to give the desired 1-alkaneselenols. The process has been used to produce 1octaneselenol on a 10.4 mol scale. Nine examples of the process are described.

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Section: Introductionmentioning

confidence: 99%

A Scalable Process for the Synthesis of 1,2-Dialkyldiselanes and 1-Alkaneselenols

Cooksey

Kocieński

Blacker

2019

Org. Process Res. Dev.

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“…Isonitriles are small and have intermediate values for transition dipoles and vibrational lifetimes, however it is unknown if these reporters will be able to be effectively incorporated into protein and nucleic acid systems. 16 Finally, thiocyanates 17,[25][26][27][28] and especially selenocyanates 29,30 have, based upon initial literature reports, 18,31 the longest vibrational lifetimes and intermediate size making them promising candidates in need of further investigation. Herein, the utility of these reporters will be expanded upon.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and evaluation of the sensitivity and vibrational lifetimes of thiocyanate and selenocyanate infrared reporters

et al. 2016

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Two novel 2′-deoxyadenosine (dA) analogues, Si2-dA-SCN and Si2-dA-SeCN, and two novel phenylalanine (Phe) analogues, Boc-Me-PheCH2SCN and Boc-Me-PheCH2SeCN, have been synthesized and the thiocyanate (SCN) and selenocyanate (SeCN) functional groups evaluated as vibrational reporters. The syntheses of Si2-dA-SCN and Si2-dA-SeCN were accomplished in three steps in 16% and 32% overall yields, respectively, and the syntheses of Boc-Me-PheCH2SCN and Boc-Me-PheCH2SeCN were completed in four steps in 8.9% and 2.3% overall yields, respectively. The SCN and SeCN stretch vibrational modes were shown to be sensitive to the local environment by frequency shifts and full-width half-maximum (fwhm) changes in response to tetrahydrofuran (THF) and THF/water solvent mixtures. The vibrational lifetimes of the Si2-dA-SeCN (237±12 ps) and Boc-Me-PheCH2SeCN (295±31 ps) in THF solution were determined by ultrafast infrared pump-probe spectroscopy to be 1.5 to 3 times longer than those for Si2-dA-SCN (140±6 ps) and Boc-Me-PheCH2SCN (102±4 ps). The longer lifetimes for the SeCN analogues were attributed to the better insulating effects of the heavier selenium atom compared to the sulfur atom. The solvent sensitivity and longer vibrational lifetimes compared to other vibrational reporters suggest that SCN and SeCN vibrational reporters are well suited to studying several dynamic processes including protein and nucleic acid hydration and conformational changes, however stability issues may require post-synthetic modification methods to incorporate these reporters into biomacromolecules.

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“…This process could even be extended to a cascade, leading to several conjugated tetrasubstituted C–C double bonds, with the delivery of the cyanide as the terminating step. Based on these insights and other reports on the Pd-catalyzed activation of chalcogenocyanates, , we asked ourselves whether an extension of this reactivity to the higher homologues, the corresponding selenocyanates, might be feasible. Besides some interesting protocols for the synthesis of highly substituted vinyl selenides, such an approach would easily grant access to tetrasubstituted selenoenol ethers (Scheme ).…”

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confidence: 99%

Pd-Catalyzed Cyanoselenylation of Internal Alkynes: Access to Tetrasubstituted Selenoenol Ethers

et al. 2020

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The intra-and intermolecular synthesis of selenium-substituted acyclic and heterocyclic acrylonitrile derivatives is presented. The 1,2-difunctionalization of several internal alkynes substituted not only by aliphatic and aromatic residues but also by heteroelements is realized by the Pd-catalyzed activation of aromatic and aliphatic selenocyanates. A high functional group tolerance allows straightforward access to a broad scope of tetrasubstituted olefins. X-ray studies of some products reveal noncovalent chalcogen−chalcogen interactions between oxygen and selenium.

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Organic Selenocyanates, Tellurocyanates and Related Compounds

Cited by 3 publications

References 195 publications

A Scalable Process for the Synthesis of 1,2-Dialkyldiselanes and 1-Alkaneselenols

A Scalable Process for the Synthesis of 1,2-Dialkyldiselanes and 1-Alkaneselenols

Synthesis and evaluation of the sensitivity and vibrational lifetimes of thiocyanate and selenocyanate infrared reporters

Pd-Catalyzed Cyanoselenylation of Internal Alkynes: Access to Tetrasubstituted Selenoenol Ethers

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