Stable Sulfonium Ylids

Ratts, K. W.; Yao, A. N.

doi:10.1021/jo01342a047

Cited by 129 publications

(31 citation statements)

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“…The treatments of the achiral analog of (-)-I, dimethylsulfonium phenacylid, 2, with acylating and alkylating agents have afforded various sulfonium compounds as depicted in Scheme 1 (19)(20)(21). The synthesis of (-)-5 and (-)-6 from (-)-I illustrates one solution to the problem associated with racemization of starting material.…”

Section: Synthesis and Reactionsmentioning

confidence: 99%

The Synthesis and Reactions of Chiral Sulfonium Ylids

Campbell¹,

Darwish²

1974

Can. J. Chem.

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Treatment of (−)-ethylmethylsulfonium phenacylid, (−)-1, in THF at room temperature with 15 equiv. of benzoic anhydride, acetic anhydride or 1 equiv. phenyl isocyanate produces the corresponding (−)-ethylmethylsulfonium diacylmethylids, (−)-5, (−)-6, and (−)-8. Treatment of (−)-1 with dimethyl sulfate in acetone gives (Z)-(+)-ethylmethyl-α-methoxy-β-styrylsulfonium methyl sulfate, (+)-10. Resolution of (±)-10 via its DBT salt and conversion to perchlorate gives the corresponding vinyl perchlorates (+)- and (−)-13. Under the resolution conditions the ketal perchlorates, (−)- and (+)-ethylmethyl-2,2-dimethoxy-2-phenylethylsulfonium perchlorate, (−)- and (+)-14, are also obtained. The rates of racemization at 50° in benzene of 1, 5, 6, and 8 are 39.7, 55.5, 106, and 79.1 × 10−5 s−1 respectively. The rates of racemization at 50° in methanol of 10, 13, and 14 are 1.93, 2.08, and 5.64 × 10−5 s−1. Racemization is proposed to proceed via pyramidal inversion. The synthetic potential of chiral sulfonium ylids is discussed with respect to their ease of racemization.

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Section: Synthesis and Reactionsmentioning

confidence: 99%

The Synthesis and Reactions of Chiral Sulfonium Ylids

Campbell¹,

Darwish²

1974

Can. J. Chem.

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“…The solid product was used as sulfonium bromide without further purification. [23] (4-(Methylthio)-5-phenylfuran-2-yl)(phenyl) methanone (3 a) Prepared according to the general procedure to afford a yellow solid in 83% yield, 61.0 mg. 1 13…”

Section: Preparation Of A-iodo Acetophenone and Sulfonium Saltsmentioning

confidence: 99%

Direct Assembly of Polysubstituted Furans via C(sp³)−H Bond Functionalization by Using Dimethyl Sulfoxide as a Dual Synthon

Liu

Cao

et al. 2019

Adv Synth Catal

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An unusual I 2 -mediated triple C(sp 3 )ÀH functionalization reaction between aryl methyl ketones and dimethyl sulfoxide to form polysubstituted furans has been developed. In this transformation, dimethyl sulfoxide functions as a dual synthon via C(sp 3 )ÀH functionalization with formation of two CÀC bonds, one CÀO bond, and one CÀS bond in a one-step process. Iodine is crucial as promoter of the reaction, by which a number of ketones could be converted easily into 2,4,5-trisubstituted furans. This provides an extremely simple and expeditious approach to high-value-added, biologically significant O-heterocycles. Based on preliminary experiments, a plausible mechanism is proposed.(4-Bromophenyl)(5-(4-bromophenyl)-4-(methylthio) furan-2-yl)methanone (3 r)Following the general procedure to afford a yellow solid in 81% yield, 85.7 mg. 1 H NMR (400 MHz, CDCl 3 ): d 7.90 (t, J = 8.4 Hz, 4H), 7.68 (d, J = 7.7 Hz, 2H), 7.60 (d, J = 7.9 Hz,

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“…To date, we have prepared and studied a total of seven sulfonium salts (Chart 1). While the preparation of each system started with the sulfenylation of either iodoacetic acid or bromoacetic acid,6 the efficacy of each salt to perform the role of alkylidene transfer agent varied greatly.…”

Section: Introductionmentioning

confidence: 99%

S-Methylidene agents: preparation of chiral non-racemic heterocycles

et al. 2009

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Reaction of sulfur ylide with aldehyde, imine, and ketone functionality affords the desired three-membered heterocycle in excellent yield. The sulfur ylide is generated in situ upon decarboxylation of carboxymethylsulfonium betaine functionality. Of the seven carboxymethylsulfonium betaine derivatives surveyed, the highest level of conversion of π-acceptor to heterocycle was obtained having S-methyl and S-phenyl functionality bound to a thioacetate derivative. Methylene aziridinations and epoxidations involving the decarboxylation of carboxymethylsulfonium betaine functionality complements existing technologies with the advantages of the reaction protocol, levels of conversion and scope. While moderate levels of diastereocontrol were observed in the aziridination of imine functionality, the four oxiranes resolved using Jacobsen’s Co(II)-salen complex were obtained in both high yield and enantioselectivity. The isolated chiral non-racemic oxiranes constitute the formal synthesis of chelonin-B and combretastatin starting from 3-bromo-4-methoxybenzaldehyde and 3,4,5-trimethoxybenzaldehyde respectively.

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Stable Sulfonium Ylids

Cited by 129 publications

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The Synthesis and Reactions of Chiral Sulfonium Ylids

The Synthesis and Reactions of Chiral Sulfonium Ylids

Direct Assembly of Polysubstituted Furans via C(sp³)−H Bond Functionalization by Using Dimethyl Sulfoxide as a Dual Synthon

S-Methylidene agents: preparation of chiral non-racemic heterocycles

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Stable Sulfonium Ylids

Cited by 129 publications

References 0 publications

The Synthesis and Reactions of Chiral Sulfonium Ylids

The Synthesis and Reactions of Chiral Sulfonium Ylids

Direct Assembly of Polysubstituted Furans via C(sp3)−H Bond Functionalization by Using Dimethyl Sulfoxide as a Dual Synthon

S-Methylidene agents: preparation of chiral non-racemic heterocycles

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Direct Assembly of Polysubstituted Furans via C(sp³)−H Bond Functionalization by Using Dimethyl Sulfoxide as a Dual Synthon