Evaluation of ethyl 2-carbomethoxyethenesulfinates as 2-hydroxymethyl enethiol equivalents in the Diels–Alder reaction

Faragher, Robert J.; Alberico, Dino; Schwan, Adrian L.

doi:10.1016/j.tet.2004.11.050

Cited by 7 publications

(8 citation statements)

References 55 publications

(51 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As such, we sought to probe the generality of the reaction, given a source of the applicable cycloadducts. 34 Initial reactions involved various Grignard reagents on the bicyclic sulfinate 2a. A number of aromatic and heteroaromatic nucleophiles were evaluated, but of those employed only p-TolMgBr demonstrated comparable reactivity, providing triaryl derivative 6 as a single diastereomer ( Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…34 The preparation of compound 18 and cycloadduct 10 is found in the Supplementary data. The preparation of the other cycloadducts has already been described.…”

Section: Methodsmentioning

confidence: 99%

“…[28][29][30][31] Diels-Alder reactions with sulfinate ester-bearing dienophiles have also been studied. [32][33][34][35] The sulfinate is particularly appealing for its ability to be readily adapted by reduction, 34,36,37 oxidation, [38][39][40] and transformation to sulfoxide. [41][42][43] Moreover, we have demonstrated that appropriately disposed sulfinate esters can participate in iodosultinization reactions with inversion of sulfinyl configuration.…”

Section: Introductionmentioning

confidence: 99%

“…32 In the current study, we examined the Grignard substitution chemistry of a series of Diels-Alder cycloadducts previously prepared from dienophile 1. 32,34 The cycloadducts bear sulfinate and carboxylate esters on vicinal carbons. It was thought that a variety of sulfoxide-based cycloadducts could be obtained from a single sulfinate by way of a series of reactions with different organometallic nucleophiles.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Unexpected reactions of Grignard reagents with selected β-carboalkoxy substituted sulfinate esters

et al. 2015

Self Cite

View full text Add to dashboard Cite

A series of six-membered rings bearing cis oriented vicinal carboxylate and sulfinate esters were treated with Grignard reagents with the intention of transforming them to ␤-carboalkoxy substituted sulfoxides. The expected outcome did not transpire and instead the substrates demonstrated the capacity to accept 3 equiv. of organometallic agent in an uncontrollable manner. As such, the substrates possessing eclipsing carboxylate and sulfinate esters accepted two organic ligands at the carboxylate functionality and one at the sulfinyl group. When isomer mixtures of sterically encumbered sulfinate esters were reacted, a single sulfoxide stereochemistry resulted. A mechanism involving the intermediacy of a sulfurane is proposed to account for the experimental observations. Résumé : Une série de cycles à six membres portant des esters carboxyliques et sulfiniques vicinaux ont été traités avec des réactifs de Grignard dans le but de les transformer en ␤-carboalkoxy sulfoxydes substitués. Le résultat espéré n'a pas été obtenu et, au lieu de cela, les substrats ont montré une capacité à accepter trois équivalents d'agent organométallique de manière incontrôlable. En tant que tels, les substrats portant des esters carboxyliques et sulfiniques en position éclipsante ont accepté deux ligands organiques au niveau de la fonction carboxylate et un au niveau du groupe sulfinyl. La réaction de mélanges isomériques d'esters sulfiniques stériquement encombrés a débouché sur une seule stéréochimie du sulfoxyde. Un mécanisme impliquant l'intermédiaire d'un sulfurane est proposé, qui permet d'expliquer les observations expérimentales. [Traduit par la Rédaction]Mots-clés : réactif de Grignard, ester sulfinique, sulfoxyde, réaction d'addition, sulfurane.

show abstract

Section: Resultsmentioning

confidence: 99%

“…34 The preparation of compound 18 and cycloadduct 10 is found in the Supplementary data. The preparation of the other cycloadducts has already been described.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Unexpected reactions of Grignard reagents with selected β-carboalkoxy substituted sulfinate esters

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…29 To a flame dried RBF was added scratched magnesium turnings (348 mg, 1.43 mmol), a crystal of iodine and THF (5 mL). 1-Bromooctane-d 17 (1.00 g, 4.76 mmol) was added dropwise and the reaction was stirred under reflux until complete formation of Grignard reagent was indicated by GC analysis (3.5 h).…”

Section: General Methodsmentioning

confidence: 99%

The preparation of three new partially deuterated hexadecanethiols for applications in surface chemistry

Sheepwash

Rowntree

Schwan

2008

Labelled Comp Radiopharmac

Self Cite

View full text Add to dashboard Cite

The synthesis of three partially deuterated hexadecanethiols has been achieved. Thiols CH 3 (CH 2 ) 7 (CD 2 ) 8 SH, CD 3 (CD 2 ) 7 (CH 2 ) 8 SH and CD 3 (CH 2 ) 15 SH were targeted, as these compounds, after formation of self-assembled monolayers on Au(1 1 1) or Au nanoparticles, can provide mechanistic information pertaining to reactive atom migrations within the assembly. The syntheses of each of these compounds called upon Grignard coupling chemistry, which was activated by Li 2 CuCl 4 . Applicable deuterium containing fragments were either commercially obtained or constructed from by way of an inexpensive and efficient ring opening, protection and dimerization of THF-d 8 . Sulfur incorporation was by thiolacetate substitution or addition reactions. The protocols presented possess general applicability in a number of syntheses requiring block-deuterated fattyalkyl sections.

show abstract

Evaluation of Ethyl 2‐Carbomethoxyethenesulfinates as 2‐Hydroxymethyl Enethiol Equivalents in the Diels—Alder Reaction.

2005

View full text Add to dashboard Cite

Cycloaddition reactions O 0070Evaluation of Ethyl 2-Carbomethoxyethenesulfinates as 2-Hydroxymethyl Enethiol Equivalents in the Diels-Alder Reaction. -Both dienophiles (I) and (V) act as masked 2-hydroxymethyl enethiol equivalents in Diels-Alder cycloaddition reactions with various dienes followed by reduction of the resulting cycloadducts. The latter are obtained as mixtures of sulfur epimers which are unified in the subsequent reduction step. Under the appropriate reaction conditions, simultaneous reduction of both the sulfinate and the carboxylate ester functionalities occurs (to be continued). -(FARAGHER, R. J.; ALBERICO, D.; SCHWAN*, A. L.; Tetrahedron 61 (2005) 5, 1115-pp; Guelph-Waterloo Cent. Grad. Work Chem., Dep. Chem. Biochem., Univ. Guelph, Guelph, Ont. N1G 2W1, Can.; Eng.) -Klein 23-039

show abstract

Evaluation of ethyl 2-carbomethoxyethenesulfinates as 2-hydroxymethyl enethiol equivalents in the Diels–Alder reaction

Cited by 7 publications

References 55 publications

Unexpected reactions of Grignard reagents with selected β-carboalkoxy substituted sulfinate esters

Unexpected reactions of Grignard reagents with selected β-carboalkoxy substituted sulfinate esters

The preparation of three new partially deuterated hexadecanethiols for applications in surface chemistry

Evaluation of Ethyl 2‐Carbomethoxyethenesulfinates as 2‐Hydroxymethyl Enethiol Equivalents in the Diels—Alder Reaction.

Contact Info

Product

Resources

About