Notes- Desulfurization of Thiiranes with Triethyl Phosphate

Schuetz, Robert D.; Jacobs, Richard L.

doi:10.1021/jo01105a618

Cited by 27 publications

(8 citation statements)

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“…The existence of 8 as an intermediate, connecting thiirane 11 and phosphorus compounds 12 with desulfurization products 4 (and 5 ), unveils the possibility of similar mechanistic consequences in other well-established desulfurization reactions of thiiranes promoted by phosphorus reagents (vide infra).…”

Section: Results and Discussionmentioning

confidence: 97%

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1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer

Ferao

Streubel

2020

Inorg. Chem.

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The potential energy surface for opening and ring-enlargement reactions of 1,2-thiaphosphetane with different oxidation states and coordination at phosphorus has been computationally explored. The most favored [2 + 2] cycloreversions are the so-called normal Wittig-type reactions furnishing an alkene and a PS-containing component. Somewhat unfavored are reactions involving the P−S bond cleavage and a C-to-P hydrogen shift as well as a ring enlargement to a 1,3,2-dithiaphospholane in the case of high coordinate derivatives. Apart from a twostep P-to-S oxygen transfer in 1,2σ 4 λ 5 -thiaphosphetane P-oxide, an interesting reaction is the P−S bond cleavage leading to a thiabetaine which, alternatively, can be formed by the C-attack of a phosphinidene oxide on a thiirane. A similar route, energetically more favored, was found for 1,2σ 5 λ 5 -thiaphosphetane starting from thiirane and the corresponding phosphane. For a wide set of P(III) reagents including HPR 2 (R = Me, Ph), PR 3 (R = Me, Ph, NMe 2 , OMe, F, Cl), and HPO, the competitive direct S-attack was found to be the preferred pathway for the desulfurization of thiiranes, and the relative tendency for these P(III) reagents to act as an S-atom acceptor, the thermodynamic S-transfer potential (TSP) scale, was defined using the S 8 /S 7 couple as a point of reference. Article pubs.acs.org/IC

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Section: Results and Discussionmentioning

confidence: 97%

“…Despite the fact that the desulfurization of thiiranes by triethylphosphite has been a well-known synthesis method since the mid-1990s, the early proposed P–S linked intermediate was ill-defined, and to the best of our knowledge, no mechanistic study has been reported since then.…”

Section: Results and Discussionmentioning

confidence: 99%

1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer

Ferao

Streubel

2020

Inorg. Chem.

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“…Aliphatic thiiranes which, on heating, tend to polymerize or dimerize rather than to decompose to olefin and sulfur can be desulfurized by interaction with trivalent organophosphorus compounds. The following phosphorus compounds are used: triphenylphosphine (39,47,53), triethylphosphine (39), triethyl phosphite (31,39,47,163,204,205), and tributylphosphine (53). With tertiary phosphines the reaction takes place readily at room temperature; gentle heating is recommended if phosphites are used.…”

Section: By Organophosphorus Compoundsmentioning

confidence: 99%

“…This suggests a nucleophilic attack of the phosphorus at the sulfur atom. The following thiiranes were subjected to the reaction: ethylene sulfide (39, 205), propene sulfide (39, 204, 205), 1-butene sulfide (53), 2-butene sulfide (163, 53), isobutene sulfide (39), 3-chloropropene sulfide (39,204,205), styrene sulfide (205), cyclohexene sulfide (39,47,205), methoxypropene sulfide (204,205), ethoxypropene sulfide (205), propoxypropene sulfide (205), isopropoxypropene sulfide (205), butoxypropene sulfide (205), phenoxy-propene sulfide (205), and diethoxypropene sulfide (205), as well as a sugar episulfide (31).…”

Section: By Organophosphorus Compoundsmentioning

confidence: 99%

Thiiranes

Sander¹

1966

Chem. Rev.

260

101

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“…The 2-alkoxymethylthiiranes were prepared from the corresponding alkyl glycidyl ethers and either aqueous potassium thiocyanate or thiourea, following experimental techniques already described. 19 Lithium aluminum hydride obtained from Metal Hydrides Incorporated, was used as received. Piperidine, morpholine, and diethylamine obtained from commercial sources were redistilled just prior to use.…”

Section: Experimental24mentioning

confidence: 99%

Reaction of 2-Alkoxymethylthiiranes with Lithium Aluminum Hydride and with Secondary Amines

Jacobs¹,

Schuetz²

1961

J. Org. Chem.

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The reduction of 2-alkoxymethylthiiranes with lithium aluminum hydride has been found to result in the formation of 1alkoxy-2-mercaptopropanes, the isomers expected from normal ring fission. The reaction of triethyl phosphite with the 1alkoxy-2-mercaptopropanes was found to result in the formation of the corresponding alkyl propyl ethers and triethyl thionophosphate. The reaction of 2-alkoxymethylthiiranes with the secondary amines, piperidine, morpholine, and diethylamine w-as also investigated. The yield of the amino mercaptan was found to be quite sensitive to the mole ratio of amine to thiirane, the nature of the product formed, the presence or absence of a solvent, and the type of solvent. The reaction of triethyl phosphite with the products isolated from the reactions of amines with 2-alkoxymethylthiiranes were found to result in the formation of amidothionophosphates and alkyl allvl ethers.

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Notes- Desulfurization of Thiiranes with Triethyl Phosphate

Abstract: Recently Scott has reported2 that the reaction of ethylene oxides with triethyl phosphite, results in the reduction of the epoxide to the corresponding olefin and oxidation of the phosphite to phosphate.

Cited by 27 publications

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1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer

1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer

Thiiranes

Reaction of 2-Alkoxymethylthiiranes with Lithium Aluminum Hydride and with Secondary Amines

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