Halogen interchange in alkyl halides using molybdenum(V) chloride

Filippo, Joseph San; Sowinski, Allan F.; Romano, Louis J.

doi:10.1021/jo00910a034

Cited by 20 publications

(6 citation statements)

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“…The resulting trihalide ion could act as an electronegative leaving group and promote the chloride substitution, showing the preferred reactivity of tertiary and secondary iodides over primary iodides. Metal chlorides such as MoCl 5 and BiCl 3 were also discovered as the role of providing the chloride source as well as activating the carbon‐halogen bond by Lewis acidic coordination to halogen leaving group. This strategy showed the 1,2‐migration phenomena in the reaction with 1‐iodooctane, supporting the intermediacy of carbocations.…”

Section: Optimization Of Conditions For Nucleophilic Chlorinationmentioning

confidence: 99%

FeCl₂‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

Hwang

Shin

Seong

et al. 2018

Bulletin Korean Chem Soc

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Alkyl halides have been considered not only important building blocks but also useful intermediates in synthetic methods of nucleophilic substitution, metal-halogen exchange, and cross-coupling reactions. As the practical synthesis of various alkyl halides, the halogen exchange is one of the fundamental and efficient reactions, which is mainly used for preparing alkyl bromides or iodides. Finkelstein-type reactions 1 have been well studied for the conversion of alkyl chlorides to the corresponding bromides or iodides and alkyl bromides to iodides, which reaction is an equilibrium shifted by taking advantage of the different solubility of the resulting sodium salt in acetone. However, the reverse processes, the replacement of iodide by bromide or chloride, or of bromide by chloride, were not simple.The early investigation on the chlorination of alkyl iodides were involved with the reaction of molecular chlorine or iodine monochloride, 2 which afforded the alkyl iodide-halogen intermediate (RIÁClX, X = Cl or I). The resulting trihalide ion could act as an electronegative leaving group and promote the chloride substitution, showing the preferred reactivity of tertiary and secondary iodides over primary iodides. Metal chlorides such as MoCl 5 3 and BiCl 3 4 were also discovered as the role of providing the chloride source as well as activating the carbon-halogen bond by Lewis acidic coordination to halogen leaving group. This strategy showed the 1,2-migration phenomena in the reaction with 1-iodooctane, supporting the intermediacy of carbocations. Another approach was the oxidativelyassisted substitution, where alkyl iodides were oxidized to iodoso compounds (RI O) by mCPBA 5 or hypervalent iodine 6 compounds for consecutive nucleophilic chlorination. In a similar way, oxidative ligand transfers between alkyl iodides and aryliodine(III) reagents produced the requisite hypervalent alkyliodine intermediates for substitution. The methods described above make the iodide a good leaving group and the modified iodine functional group cannot act as a nucleophile again. On the other hand, a process of separating the generated alkyl chlorides by boiling point difference 7 or separating the leaving iodide into fluorous phase using fluorous phosphonium salt has been developed. 8

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Section: Optimization Of Conditions For Nucleophilic Chlorinationmentioning

confidence: 99%

FeCl₂‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

Hwang

Shin

Seong

et al. 2018

Bulletin Korean Chem Soc

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“…In general, molybdenum pentachloride can be employed for the chlorination of alkyl halides,1 alkenes2 and alkynes (Scheme ) 3…”

Section: Mov Reagents For Chlorinationmentioning

confidence: 99%

“…The alkyl chlorides are reported in yields of up to 71 % 1. The reaction can be employed for the transformation of secondary and tertiary alkyl fluorides, bromides and iodides into the corresponding chlorides.…”

Section: Mov Reagents For Chlorinationmentioning

confidence: 99%

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Mo^V Reagents in Organic Synthesis

Schubert

Waldvogel

2016

Eur J Org Chem

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The use of Mo V reagents, and in particular MoCl 5 , in organic synthesis is surveyed. The oxidative treatment of aromatic substrates is the most common application. The unique properties of these reagents are due to their high oxidative power combined with exquisite Lewis acid properties. In several examples Mo V reagents outperform other common oxidative coupling reagents. C-C bond formation through inter-and intramolecular oxidative coupling can lead to selective formation of five-to eight-membered ring systems. Mechanistic investigations of the courses of reactions involving Mo V reagents and aromatic substrates indicate that radical cations are initially

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“…The halogen exchange of alkyl and aryl halides is a fundamental reaction in pharmaceutical and agrochemical industries. [1][2][3][4] The alkyl and aryl halide functional groups can readily be used in a wide range of cross-coupling reactions, 5 organometallic reagents, 6 physical and biological properties modication of aromatic rings 7,8 and generation of freeradical intermediates precursor. 1,9 Gas phase halogen exchange is mainly used for preparing alkyl bromides or iodides, which are more reactive and can be readily employed in numerous transformations.…”

Section: Introductionmentioning

confidence: 99%

Facile continuous process for gas phase halogen exchange over supported alkyl phosphonium salts

Sharma

Sasson

2018

RSC Adv.

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Halogen interchange in alkyl halides using molybdenum(V) chloride

Cited by 20 publications

References 0 publications

FeCl₂‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

FeCl₂‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

Mo^V Reagents in Organic Synthesis

Facile continuous process for gas phase halogen exchange over supported alkyl phosphonium salts

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Halogen interchange in alkyl halides using molybdenum(V) chloride

Cited by 20 publications

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FeCl2‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

FeCl2‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

MoV Reagents in Organic Synthesis

Facile continuous process for gas phase halogen exchange over supported alkyl phosphonium salts

Contact Info

Product

Resources

About

FeCl₂‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

FeCl₂‐mediated Nucleophilic Chlorination of Iodoalkanes Accelerated by Phenanthroline Ligand

Mo^V Reagents in Organic Synthesis