New Organic Chemistry of Sulfur Dioxide

Vogel, Pierre; Turks, Māris; Bouchez, Laure C.; Marković, Dean; Varela‐Álvarez, Adrián; Sordo, José

doi:10.1021/ar700096h

Cited by 123 publications

(76 citation statements)

References 75 publications

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“…[60][61][62][63][64] Neopentyl 1 H NMR spectra of the crude reaction mixtures, they were all better than 50%. In all cases the linear product 5a was favored (product of no allylic rearrangement).…”

Section: Resultsmentioning

confidence: 95%

Palladium-catalyzed desulfinylative C–C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters

Volla¹,

Dubbaka²,

Vogel³

2009

Tetrahedron

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a b s t r a c t 2-Methylprop-2-ene-, prop-2-ene-, 1-methylprop-2-ene-, and (E)-but-2-enesulfonyl chlorides have been used as electrophilic partners in desulfinylative palladium-catalyzed C-C coupling with Grignard reagents and sodium salts of dimethyl malonate and methyl acetoacetate. Neopentyl alk-2-ene sulfonates can also be used as electrophilic partners in desulfinylative allylic arylations and allylic alkylations. The regioselectivity of the allylic arylation and alkylation depends on the nature of the catalyst. With PdCl 2 (PhCN) 2 , (E)-crotyl derivatives are formed in high regioselectivity using either 1-methylprop-2-eneor (E)-but-2-enesulfonyl chloride.

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Section: Resultsmentioning

confidence: 95%

Palladium-catalyzed desulfinylative C–C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters

Volla¹,

Dubbaka²,

Vogel³

2009

Tetrahedron

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“…In situ oxidation of sulfinates 14 with Cl 2 or NCS provides the corresponding sulfonyl chlorides that can be reacted with primary and secondary amines to provide the corresponding sulfonamides 17, thus realizing a one-pot, four-component synthesis of polyfunctional suflonamides [60,61]. We review here applications of our reaction cascade 9 + SO 2 → 10 → 12 + 13 → 14 → 15 to the asymmetric total synthesis of polypropionate antibiotics [62] and disclose further chemistry of sultines with allylsilanes [63].…”

Section: Introductionmentioning

confidence: 97%

“…Our studies have been reviewed [42][43][44][45]. Apart from sultines resulting from reactions of SO 2 with 1-fluoro-1,3-dienes [46], sultines are less stable than their sulfolene isomers.…”

Section: Introductionmentioning

confidence: 99%

Use of sultines in the asymmetric synthesis of polypropionate antibiotics

Vogel

Turks

Bouchez

et al. 2008

Pure and Applied Chemistry

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At low temperature and in the presence of an acid catalyst, SO 2 adds to 1,3-dienes equilibrating with the corresponding 3,6-dihydro-1,2-oxathiin-2-oxides (sultines). These compounds are unstable above -60°C and equilibrate with the more stable 2,5-dihydrothiophene 1,1-dioxides (sulfolenes). The hetero-Diels-Alder additions of SO 2 are suprafacial and follow the Alder endo rule. The sultines derived from 1-oxy-substituted and 1,3-dioxydisubstituted 1,3-dienes cannot be observed at -100°C but are believed to be formed faster than the corresponding sulfolenes. In the presence of acid catalysts, the 6-oxy-substituted sultines equilibrate with zwitterionic species that react with electron-rich alkenes such as enoxysilanes and allylsilanes, generating β,γ-unsaturated silyl sulfinates that can be desilylated and desulfinylated to generate polypropionate fragments containing up to three contiguous stereogenic centers and an (E)-alkene unit. Alternatively, the silyl sulfinates can be reacted with electrophiles to generate polyfunctional sulfones (one-pot, four-component synthesis of sulfones), or oxidized into sulfonyl chlorides and reacted with amines, then realizing a one-pot, four-component synthesis of polyfunctional sulfonamides. Using enantiomerically enriched dienes such as 1-[(R)-or 1-(S)-phenylethyloxy]-2-methyl-(E,E)-penta-1,3-dien-3-yl isobutyrate, derived from inexpensive (R)-or (S)-1-phenylethanol, enantiomerically enriched stereotriads are obtained in one-pot operations. The latter are ready for further chain elongation. This has permitted the development of expeditious total asymmetric syntheses of important natural products of biological interest such as the baconipyrones, rifamycin S, and apoptolidin A.

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“…Indeed, its utility in pericyclic reactions has been widely applied in natural product synthesis and reviewed recently. [8] Other notable reactions include co-polymerisation with alkenes to form sulfone polymers, [9] and addition to organometallic species yielding metal sulfinate salts (Scheme 1). [10] However, despite the frequent occurrence of sulfonyl-derived functional groups such as sulfones and sulfonamides as intermediates or synthetic targets, the disconnection of these molecules back to SO 2 gas is rarely suggested during retrosynthetic analysis.…”

Section: Sulfur Dioxide: An Introductionmentioning

confidence: 99%

The Development and Application of Sulfur Dioxide Surrogates in Synthetic Organic Chemistry

2015

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Sulfur dioxide has a rich and varied chemistry that can be traced back to the early 1900s. Despite the potential utility of sulfur dioxide based reactions, delivering products such as sulfones, sulfonamides and sulfinic acids, the number of examples of these reactions being exploited in synthesis is arguably lower than would be expected. One significant contributing factor to this is undoubtedly the toxic and gaseous nature of SO2. One strategy to overcome this limitation is to employ an equivalent, or surrogate, so that the gaseous reagent is no longer needed. This strategy has proven to be a success, with a number of methods being described. The reactions reported include variants of traditional reactions in which the gaseous reagent has been replaced with a surrogate, and also new transformations for which no gaseous reaction is known. This Focus Review discusses the origin of sulfur dioxide surrogates and then considers their application to synthetic organic chemistry.

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New Organic Chemistry of Sulfur Dioxide

Cited by 123 publications

References 75 publications

Palladium-catalyzed desulfinylative C–C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters

Palladium-catalyzed desulfinylative C–C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters

Use of sultines in the asymmetric synthesis of polypropionate antibiotics

The Development and Application of Sulfur Dioxide Surrogates in Synthetic Organic Chemistry

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