Derivatives of Aromatic Sulfinic Acids. III. Evidence for the Hydrogen Dichloride Ion from Epimerization Reactions<sup>1</sup>

Herbrandson, Harry F.; Dickerson, Richard T.

doi:10.1021/ja01524a070

Cited by 43 publications

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“…Oxidation of 31 with 30% H 2 O 2 led to 29 . The synthesis of enantiomerically enriched ( R )- 28 (64% ee) (vide infra) was accomplished by reaction of lithiated diphenyl- o -tolylphosphine with enantiomerically enriched menthyl benzenesulfinate. , …”

Section: Resultsmentioning

confidence: 99%

Endocyclic Restriction Test: Applications to Transfers of Oxygen from Nitrogen and from Sulfur to Phosphorus(III)

Kurtzweil

Beak

1996

J. Am. Chem. Soc.

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The geometries allowed for formal transfers of oxygen to the phosphorus(III) of a phosphine from a nitrone, an O-acetylhydroxylamine, and a sulfoxide have been evaluated by the endocyclic restriction test. Investigations of the conversions of 1 to 2, 16 to 17, and 28 to 29, by isotopic labeling, substituent effect, and kinetic and spectroscopic experiments, reveal the operation of different mechanisms for each of these transfers. For 1, oxygen addition to phosphorus is the preferred mechanism. In the case of 16, the mechanism involves nucleophilic displacement of oxygen from nitrogen by phosphorus to give 26 followed by oxygen addition to phosphorus. In acetic acid, the oxygen is added to 26 from water in the workup whereas in toluene the oxygen is provided by the acetate produced by the displacement. For 28, either addition by oxygen of the sulfoxide to activated phosphorus or addition by phosphorus to sulfur of the sulfoxide precedes oxygen transfer.

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Section: Resultsmentioning

confidence: 99%

Endocyclic Restriction Test: Applications to Transfers of Oxygen from Nitrogen and from Sulfur to Phosphorus(III)

Kurtzweil

Beak

1996

J. Am. Chem. Soc.

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“…[8][9][10][11][12] Usually, this heterocyclic 2-oxide system can be smoothly obtained from the treatment of N-alkyl/aryl amino alcohol with thionyl chloride. [8][9][10][11][12][13][14][15][16][17][18] Thus, what has to be specially noted is that the reaction of 11~13 shown in Scheme II demonstrates, to the best of our knowledge, the first example of using mesyl chloride instead of thionyl chloride as the re-source of sulfoxide (S=O) moiety for 1,2,3-ozathiazolidine-2-oxide system. The mechanism for this reaction, which afforded the originally unexpected new product(s), is illustrated in Figure 5.…”

Section: Resultsmentioning

confidence: 99%

Condensation‐ring Expansion Reaction of Formyl[2.2.1]bicyclic Carbinols with Para‐substituted Phenyl Amines: Application to the Preparation of [3.2.1]bicyclic N‐aryl‐1,2,3‐oxathiazolidine‐2‐oxide Agents

Yang

Chen

Kao

et al. 2012

J Chinese Chemical Soc

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Individual reaction of camphene-derived endo-formyl [2.2.1]bicyclic carbinol and that of camphor-derived exo-formyl[2.2.1]bicyclic carbinol with parent and para-substituted phenyl amines gave regio-and stereospecific corresponding [3.2.1]bicyclic (para-substituted) phenyl amino ketones. Mechanism of each reaction was discussed. Some camphor-derived [3.2.1]bicyclic amino ketones were reduced to [3.2.1]bicyclic (para-substituted) phenyl amino alcohols, which were then treated with mesyl chloride to provide [3.2.1]bicyclic N-phenyl/aryl-1,2,3-oxathiazolidine-2-oxide agents. The mechanism of this final reaction was discussed as well.

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“…After a few days a white precipitate (diphenyl disulfide) appeared. The reaction was continued for 35 days. Then the solution was neutralized with sodium carbonate and extracted several times with chloroform.…”

Section: Methodsmentioning

confidence: 99%

Novel route to racemization of sulfoxides

Modena¹,

Quintily²,

Scorrano³

1972

J. Am. Chem. Soc.

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Derivatives of Aromatic Sulfinic Acids. III. Evidence for the Hydrogen Dichloride Ion from Epimerization Reactions¹

Cited by 43 publications

References 0 publications

Endocyclic Restriction Test: Applications to Transfers of Oxygen from Nitrogen and from Sulfur to Phosphorus(III)

Endocyclic Restriction Test: Applications to Transfers of Oxygen from Nitrogen and from Sulfur to Phosphorus(III)

Condensation‐ring Expansion Reaction of Formyl[2.2.1]bicyclic Carbinols with Para‐substituted Phenyl Amines: Application to the Preparation of [3.2.1]bicyclic N‐aryl‐1,2,3‐oxathiazolidine‐2‐oxide Agents

Novel route to racemization of sulfoxides

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Derivatives of Aromatic Sulfinic Acids. III. Evidence for the Hydrogen Dichloride Ion from Epimerization Reactions1

Cited by 43 publications

References 0 publications

Endocyclic Restriction Test: Applications to Transfers of Oxygen from Nitrogen and from Sulfur to Phosphorus(III)

Endocyclic Restriction Test: Applications to Transfers of Oxygen from Nitrogen and from Sulfur to Phosphorus(III)

Condensation‐ring Expansion Reaction of Formyl[2.2.1]bicyclic Carbinols with Para‐substituted Phenyl Amines: Application to the Preparation of [3.2.1]bicyclic N‐aryl‐1,2,3‐oxathiazolidine‐2‐oxide Agents

Novel route to racemization of sulfoxides

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Derivatives of Aromatic Sulfinic Acids. III. Evidence for the Hydrogen Dichloride Ion from Epimerization Reactions¹