Direct 1,5-cycloaddition of sulphur dioxide to cyclo-octatetraene. 9-Thiabarbaralane 9,9-dioxide

Paquette, Leo A.; Jacobsson, Ulla; Oku, Masayoshi

doi:10.1039/c39750000115

Cited by 17 publications

(4 citation statements)

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“…Organic chemistry of SO 2 has been limited to the Friedel–Crafts sulfinylation, copolymerization of SO 2 with alkenes and alkynes, the synthesis of sulfinates and sulfones from polar organometallic species, the ring opening of epoxides and oxetanes leading to polysulfites, the isomerization of alkenes, and the formation of sulfolenes by cheletropic additions with 1,3-dienes (for examples of classical organic reactions of sulfur dioxide reviews, see ref and refs 1–13 cited therein; see also refs and ), a reaction reported first in 1914 . Other cycloadditions of SO 2 have been described for the reaction of ketenes and ketimines, – cyclic polyenes, , and quadricyclane . Homocheletropic additions of SO 2 to 1,4-dienes have been reported. – The first examples of hetero-Diels–Alder additions of SO 2 involved highly reactive dienes 1 and 3 .…”

Section: Introductionmentioning

confidence: 99%

New Organic Chemistry of Sulfur Dioxide

et al. 2007

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Simple 1,3-dienes undergo highly stereoselective hetero-Diels-Alder additions with SO2 at low temperature giving sultines. These reactions that are faster than the more exothermic cheletropic additions of SO2-producing sulfolenes. This has led to the invention of a new C-C bond-forming reaction combining electron-rich dienes and alkenes with SO2. The reaction cascade has been exploited to develop combinatorial, one-pot, four-component syntheses of polyfunctional sulfones, sulfonamides, and sulfonic esters. It also allows us to generate, in one-pot operations, enantiomerically enriched polypropionate fragments containing up to three contiguous stereogenic centers and a (E)-alkene unit. These fragments can be used directly in further C-C bond-forming reactions, such as cross-aldol condensations, thus permitting the expeditious construction of complicated natural products of biological interest (e.g., Baconipyrones, Rifamycin S, Apoptolidinone) and analogues. New ene reactions of SO2 have also been discovered; they open new avenues to organic synthesis.

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Section: Introductionmentioning

confidence: 99%

New Organic Chemistry of Sulfur Dioxide

et al. 2007

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“…Other cycloadditions of SO 2 have been described for the reaction of ketenes and ketimines [28][29][30][31], cyclic polyenes [32][33][34], and quadricyclane [35]. Homocheletropic additions of SO 2 to 1,4-dienes have been reported [36][37][38].…”

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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“…Although sulfur dioxide has been used for a long time as food and beverage preservative, the organic chemistry of SO 2 has been limited to the Friedel-Crafts sulfinylation, 38,39 copolymerization of SO 2 with alkenes and alkynes, [40][41][42][43][44][45] the synthesis of sulfinates and sulfones from polar organometallic species, [46][47][48] the ring opening of epoxides and oxetanes 49 leading to polysulfites, 50,51 the isomerization of alkenes, [52][53][54][55] and the formation of sulfolenes by cheletropic additions with 1,3-dienes. [56][57][58][59][60][61] Other cycloadditions of SO 2 have been described for the reaction of ketenes and ketimines, [62][63][64][65][66][67][68] cyclic polyenes, 69 and quadricyclane. [70][71][72] In 1992, we reported that simple 1,3-dienes undergo hetero-Diels-Alder addition below -60°C in the presence of a large excess of SO 2 and of a protic or Lewis acid promoter (Scheme 11).…”

Section: Introductionmentioning

confidence: 99%

Umpolung with Sulfur Dioxide: Carbon-Carbon Cross-Coupling of Electron-Rich 1,3-Dienes and Alkenes; Application to the Enantioselective Synthesis of Long-Chain Polyketide Fragments

Turks¹,

Exner²,

Hamel³

et al. 2009

Synthesis

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At low temperature and in the presence of an acid catalyst, sulfur dioxide undergoes hetero-Diels-Alder additions with 1-oxy-1,3-dienes, giving unstable sultines, which are ionized into zwitterionic species and react as 1-oxyallylic cation intermediates (Umpolung with SO 2) with electron-rich alkenes such as allylsilanes or enoxysilanes. The b,g-unsaturated silyl sulfinates so-obtained can be desulfinylated in situ to generate polyketide fragments containing up to three contiguous stereogenic centers in one-pot operations. This reaction cascade can be applied in two-directional chain elongation approaches for the asymmetric synthesis of long chain polyketide fragments using 1-[(S)-or (R)-1-phenylethoxy]-1,3-dienes.

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Direct 1,5-cycloaddition of sulphur dioxide to cyclo-octatetraene. 9-Thiabarbaralane 9,9-dioxide

Cited by 17 publications

References 0 publications

New Organic Chemistry of Sulfur Dioxide

New Organic Chemistry of Sulfur Dioxide

Use of sultines in the asymmetric synthesis of polypropionate antibiotics

Umpolung with Sulfur Dioxide: Carbon-Carbon Cross-Coupling of Electron-Rich 1,3-Dienes and Alkenes; Application to the Enantioselective Synthesis of Long-Chain Polyketide Fragments

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