Sulfur dioxide mediated one-pot, four-component synthesis of polyfunctional sulfones and sulfonamides, including medium-ring cyclic derivatives

Bouchez, Laure C.; Turks, Māris; Dubbaka, Srinivas Reddy; Fonquerne, Freddy; Craita, Cotinica; Laclef, Sylvain; Vogel, Pierre

doi:10.1016/j.tet.2005.08.067

Cited by 26 publications

(6 citation statements)

References 154 publications

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“…The polypropionate fragments 15 so-obtained have their two extremities ready for further chain elongation without requiring deprotection and activation. Alternatively, the intermediate sulfinates 14 can be converted in the same pot into sulfones 16, thus realizing a one-pot, four-component synthesis of polyfunctional sulfones [56][57][58][59][60]. 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].…”

Section: Introductionmentioning

confidence: 99%

“…Alternatively, the intermediate sulfinates 14 can be converted in the same pot into sulfones 16, thus realizing a one-pot, four-component synthesis of polyfunctional sulfones [56][57][58][59][60]. 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: 99%

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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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Section: Introductionmentioning

confidence: 99%

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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“…In addition, the electrophilic nature of sulfur dioxide has seen it utilized in the synthesis of sulfinates, and related sulfones, from combination with nucleophilic organometallic species such as Grignard reagents and organolithiums . More recently, it has found application in multicomponent systems, leading to the synthesis of complex polyfunctionalized molecules . Despite this varied reactivity profile, and the corresponding range of compounds that can be prepared, the number of applications of these reactions in synthesis is arguably lower than would be expected.…”

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confidence: 99%

DABCO-Bis(sulfur dioxide), DABSO, as a Convenient Source of Sulfur Dioxide for Organic Synthesis: Utility in Sulfonamide and Sulfamide Preparation

et al. 2011

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The charge-transfer complex generated from the combination of DABCO and sulfur dioxide, DABSO, is a bench-stable colorless solid suitable for use in organic synthesis as a replacement for gaseous sulfur dioxide. The complex can be combined with Grignard reagents to form sulfinates, which can then be converted in situ to a series of sulfonamides. Alternatively, reaction with anilines and iodine leads to the formation of a series of sulfamides. Cheletropic addition between DABSO and 2,3-dimethylbutadiene provides the corresponding sulfolene.

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“…Changing the retro-ene reaction conditions to a more acidic buffer system led to the isolation of 21 as the only product (Table 1, entry 2). [15,16] Products of [c] -< 5 (ent) [c] [a] This result has been previously published, see Turks et al [10] [b] A racemic mixture of the two enantiomers of this compound was obtained. [c] The opposite enantiomer than the one shown was obtained.…”

Section: Resultsmentioning

confidence: 58%

Concise Synthesis of Complicated Polypropionates through One‐Pot Dissymmetrical Two‐Directional Chain Elongation

Exner

Turks

Fonquerne

et al. 2011

Chemistry A European J

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Herein, a major breakthrough in a sulfur dioxide-mediated oxyallylation cascade reaction is reported that allows the preparation of complex long-chain polyketide fragments with more than ten stereogenic centers through a carefully designed desymmetrization process. An allylbissilane is combined, under the appropriate reaction conditions, with two different 1,3-dioxy-1,3-dienes permitting the construction of a 13-membered polypropionate precursor in one pot. Four stereocenters are selectively created during this process. The so-obtained pseudo-C(2)- or -C(S)-symmetric products are desymmetrized through selective deprotection and can be selectively elongated in both directions using aldol chemistry.

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Sulfur dioxide mediated one-pot, four-component synthesis of polyfunctional sulfones and sulfonamides, including medium-ring cyclic derivatives

Cited by 26 publications

References 154 publications

Use of sultines in the asymmetric synthesis of polypropionate antibiotics

Use of sultines in the asymmetric synthesis of polypropionate antibiotics

DABCO-Bis(sulfur dioxide), DABSO, as a Convenient Source of Sulfur Dioxide for Organic Synthesis: Utility in Sulfonamide and Sulfamide Preparation

Concise Synthesis of Complicated Polypropionates through One‐Pot Dissymmetrical Two‐Directional Chain Elongation

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