Syntheses of<i>gem</i>-Dihalocyclopropanes and Their Use in Organic Synthesis

Fedoryński, M.

doi:10.1021/cr0100087

Cited by 321 publications

(154 citation statements)

References 380 publications

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“…Emulsion problems often reported to occur during workup [40] was under the conditions reported herein, only an issue for 1,1-dibromo-2-(chloromethyl)-2-methylcyclopropane (9).…”

Section: Discussionmentioning

confidence: 68%

“…However, since the gem-dibromocyclopropanes are reported to be generally more reactive than the corresponding gemdichlorocyclopropanes [9] and, thus, are more interesting as intermediates in organic synthesis, we focused our attention on the gem-dibromocompounds and did not elaborate further along synthesizing the dichlorocompounds.…”

Section: Resultsmentioning

confidence: 99%

“…They have also been found useful in the syntheses of many natural products, as emphasized in several reviews [9][10][11]. New methods for their exploitation are still under development [11].…”

Section: Introductionmentioning

confidence: 99%

“…The phase-transfer catalyzed two-phase dihalocyclopropanation of alkenes, since its discovery by Makosza [12], has become a well-established, widely used method in organic synthesis, and is still one of the most effective methods for preparation of gem-dibromocyclopropanes [9,11,13].…”

Section: Introductionmentioning

confidence: 99%

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The Use of Flow Chemistry for Two-Phase Dibromocyclopropanation of Alkenes

Østby¹,

Stenstrøm²,

Didriksen³

2015

J Flow Chem

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Conventional batch dibromocyclopropanations by reaction of bromoform and alkenes under phase-transfer conditions require strong base (50% NaOH (aq)), vigorous stirring, and often long reaction times. Using flow chemistry in a microreactor, the reactions were found to be smooth, rapid, and high-yielding under ambient conditions when 40% (w/w) NaOH was used as the base. The reaction has been tested with a representative selection of alkenes, displaying a variety of structural features.

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“…Emulsion problems often reported to occur during workup [40] was under the conditions reported herein, only an issue for 1,1-dibromo-2-(chloromethyl)-2-methylcyclopropane (9).…”

Section: Discussionmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Use of Flow Chemistry for Two-Phase Dibromocyclopropanation of Alkenes

Østby¹,

Stenstrøm²,

Didriksen³

2015

J Flow Chem

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“…[1][2][3][4][5][6][7][8][9][10][11] These compounds are excellent building blocks due to their availability in high enantiomeric purity, simple techniques of preparation, and a substantial synthetic potential of the cyclopropane ring. [12][13][14][15] For example, they were utilized in the asymmetric synthesis of pyrethroids 1,2 and other natural products, 3,4 stereoregular oligocyclopropanes, 5 chiral biaryls, 6 and liquid crystals. 7 In a recent article we efficiently resolved racemic trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid into enantiomers 1.…”

Section: Introductionmentioning

confidence: 99%

Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Kovalenko¹

2013

Arkivoc

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Substitution of the β-halogen atoms in methyl (1R,3S)-2,2-dichloro-3-methylycyclopropanecarboxylate with sodium thiophenolate leads to the di(phenylthio) ester (1RS,3S)-4 as a mixture of diastereomers. The cis-trans isomerisation of methyl (1RS,3S)-3-methyl-2,2-bis(phenylthio)-cyclopropanecarboxylate 4, basic hydrolysis and subsequent crystallization gave the corresponding acid (1R,3S)-5 in high diastereomeric and enantiomeric purity. On the other hand, ring opening of the ester (1RS,3S)-4 under acidic conditions leads to methyl 3-methyl-4,4-di(phenylthio)prop-3-enoate (8) or the chiral S-phenyl thioester methyl (3S)-3-methyl-4-oxo-4-(phenylthio)butanoate (7).

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Phase Transfer Catalysis

Mąkosza

Fedoryński

2010

Encyclopedia of Catalysis

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Basic concept of phase transfer catalysis (PTC), specific features of this general methodology for executing organic reactions, and mechanism of catalytic action of PT catalysts are presented. Scope and limitations of application of PTC as a general tool of organic synthesis and advantages offered by this methodology are discussed. These discussions are illustrated by numerous examples of successful use of PTC in a variety of reactions of inorganic anions (substitution and addition reactions, β‐eliminations, oxidations, and reductions), heteroanions, and particularly carbanions (reactions with alkylating agents, carbonyl groups, activated carbon‐carbon multiple bonds, electrophilic arenes, heteroatom electrophiles) and carbenes. Possibility of use of PTC for reactions of metalloorganic compounds and complexes and for enantioselective reactions is discussed.

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Syntheses ofgem-Dihalocyclopropanes and Their Use in Organic Synthesis

Cited by 321 publications

References 380 publications

The Use of Flow Chemistry for Two-Phase Dibromocyclopropanation of Alkenes

The Use of Flow Chemistry for Two-Phase Dibromocyclopropanation of Alkenes

Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Phase Transfer Catalysis

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