Rearrangements of 2-phenylthioethanols with alkenyl, alkynyl, ester, and other functionalised alkyl substituents at the migration origin: synthesis of γ-phenylthiocrotonate esters

Brownbridge, Peter; Hunt, Paul G.; Warren, Stuart

doi:10.1039/p19860001695

Cited by 4 publications

(2 citation statements)

References 11 publications

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“…( E ) - ( R )-3-Methoxycarbonyl-1-methyl-2-butenyl Phenyl Sulfide (10). 2.7 g ( R )-2-Phenylsulfanylpropionate ( 9 ) (14 mmol) was dissolved in 50 mL of dry CH 2 Cl 2 and cooled to −78 °C. A 16 mL portion of Dibal-H (16 mmol, 1 N in hexane) was added dropwise.…”

Section: Methodsmentioning

confidence: 99%

Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

Bach

Körber

2000

J. Org. Chem.

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Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN3) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples). Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to alpha-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% ee). A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)3/NEt3 in CH2Cl2 (three examples, 43-62% yield).

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Section: Methodsmentioning

confidence: 99%

Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

Bach

Körber

2000

J. Org. Chem.

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“…(E)-Ethyl 4-(phenylthio)but-2-enoate (3): [12] A 2.05 mL portion of thiophenol (2.2 g, 20 mmol) and 5.13 g of (E)-ethyl 4-bromobut-2-enoate (22 mmol) were dissolved in 30 mL of dry diethyl ether and cooled to -10 ℃. A 2.2 g portion of triethylamine (22 mmol) was added dropwise during 0.5 h. After being stirred at -10 ℃ for 30 min, the mixture was refluxed for 1 h and stirred overnight at room temperature.…”

Section: Synthesis and Spectral Data For The Substrates 1a-1q And 3-4mentioning

confidence: 99%

Catalyst‐Free Imidation of Allyl Sulfides with Chloramine‐T and Subsequent [2,3]‐Sigmatropic Rearrangement

Jiang¹,

Mo²,

Qiu³

et al. 2012

Chin. J. Chem.

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A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within 10 min, providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.

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2,3-Dichloropropene

Cherry

2001

Encyclopedia of Reagents for Organic Synthesis

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Rearrangements of 2-phenylthioethanols with alkenyl, alkynyl, ester, and other functionalised alkyl substituents at the migration origin: synthesis of γ-phenylthiocrotonate esters

Cited by 4 publications

References 11 publications

Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

Catalyst‐Free Imidation of Allyl Sulfides with Chloramine‐T and Subsequent [2,3]‐Sigmatropic Rearrangement

2,3-Dichloropropene

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