Chlorination of cyclopentadiene and 1,3-cyclohexadiene with iodobenzene dichloride and trichloramine

Heasley, Victor L.; Rold, Kerry D.; McKee, David B.; Heasley, Gene E.

doi:10.1021/jo00869a056

Cited by 14 publications

(21 citation statements)

References 2 publications

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“…162 A related question has arisen in ionic mechanisms with PhICl 2 as to whether Cl − or Ph(Cl)I − is the active nucleophile ( vide infra ). 115,159,163 …”

Section: Alkene Dihalogenations With Main Group Halides As Reagentmentioning

confidence: 99%

“…165 In all of these cases, the simple (internal) diastereoselectivity is explained on the basis of steric interactions between the β-chloro radical intermediate and PhICl 2 as a very bulky chlorine atom donor. 115,161,164,165 …”

Section: Alkene Dihalogenations With Main Group Halides As Reagentmentioning

confidence: 99%

“…[157] In general, dichlorinations of alkenes with PhICl 2 in chlorocarbon solvents follow either ar adical chain mechanism (Type V) or an ionic mechanism (Type Io rT ype II), depending on the reaction conditions. [115,158,159] Ther adical chain mechanism (Scheme 51), originally proposed by Bloomfield, [160] can be initiated either thermally or photochemically (in the absence of radical inhibitors such as oxygen), and support for this mechanism comes from studies of certain alkenes as mechanistic probes for ionic versus radical dichlorination, including norbornene, [24b,121, 158, 159] cyclooctene, [126] cyclooctadienes, [107,121] cyclopentadiene and 1,3-cyclohexadiene, [115] vinylcyclopropanes, [116] and others. [159] By analogy to radical dichlorinations with SO 2 Cl 2 (see above), [142] it has been proposed that ClC is the chain-carrying radical, [158,159] although Ph(Cl)IC could also be the chaincarrier.…”

Section: Iodinementioning

confidence: 99%

“…[162] Ar elated question has arisen in ionic mechanisms with PhICl 2 as to whether Cl À or Ph(Cl)I À is the active nucleophile (see above). [115,159,163] Regarding the stereochemical course of these radical dichlorinations,m ixtures of anti-a nd syn-dichlorination products are frequently obtained, which for cyclic alkenes typically (though not always) favor the anti-diastereomer. [121,126,158,164] High stereoselectivity can even be obtained with acyclic alkenes: b-methylstyrenes 51 and 52,for example, give 92:8 and 91:9 ratios of anti-53/syn-54 dichlorides, respectively,u pon photoinitiated reaction with PhICl 2 (Scheme 52).…”

Section: Iodinementioning

confidence: 99%

See 3 more Smart Citations

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

2015

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Although recent years have witnessed significant advances in the development of catalytic, enantioselective halofunctionalizations of alkenes, the related dihalogenation of olefins to afford enantioenriched vicinal dihalide products remains comparatively underdeveloped. However, the growing number of complex natural products bearing halogen atoms at stereogenic centers has underscored this critical gap in the synthetic chemist's arsenal. This Review highlights the selectivity challenges inherent in the design of enantioselective dihalogenation processes, and formulates a mechanism-based classification of alkene dihalogenations, including those that may circumvent the "classical" haliranium (or alkene-dihalogen π-complex) intermediates. A variety of metal and main group halide reagents that have been used for the dichlorination or dibromination of alkenes are discussed, and the proposed mechanisms of these transformations are critically evaluated. AbstractCatalysis of alkene dihalogenation , under different activation modes, with control over both the absolute and relative stereochemical course of dihalogen addition, is one of the most vexing problems in stereoselective synthesis. Dihalogenations that circumvent the "classical" haliranium (or alkene-dihalogen π complex) intermediates provide new and exciting opportunities for catalysis, potentially having broader implications for the design of stereoselective alkene difunctionalizations.

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“…162 A related question has arisen in ionic mechanisms with PhICl 2 as to whether Cl − or Ph(Cl)I − is the active nucleophile ( vide infra ). 115,159,163 …”

Section: Alkene Dihalogenations With Main Group Halides As Reagentmentioning

confidence: 99%

Section: Alkene Dihalogenations With Main Group Halides As Reagentmentioning

confidence: 99%

Section: Iodinementioning

confidence: 99%

Section: Iodinementioning

confidence: 99%

See 2 more Smart Citations

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

2015

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“…Treating alkenes 2 with 1 in chlorocarbon solvents produces, for example, the vicinal dichloro products anti ‐ 4 with a high anti selectivity, hinting at a type I mechanism proceeding via the chloriranium ion 3 . This intermediate 3 is then most likely opened by Ph(Cl)I − , rather than Cl − as the pendant nucleophile, often leading to higher diastereoselectivities for 1 in comparison to Cl 2 as the chlorinating agent . A possible alternate mechanism leading to the anti product 4 involves the attack of the double bond in 2 at the iodine(III) atom in 1 , generating the iodiranium compound 5 (type II).…”

Section: General Aspects Of Hypervalent Iodine(iii)‐mediated Halogenamentioning

confidence: 99%

Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

Arnold

Ulmer

Gulder

2016

Chemistry A European J

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Within the repertoire of organic chemical transformations, the halogenation of substrates is among the most versatile, reliable, and broadly applicable reactions. Although a multitude of different methods are known today, there is still a huge demand for novel and, in particular, catalytic halogenation methods that exhibit new reactivities and selectivities. The class of hypervalent iodanes meets exactly these needs and thus offers a great opportunity to fuel this highly desirable direction within the field of halogenation chemistry. This Concept gives a short overview of recent examples focusing on selective and/or mechanistically unusual halogenations.

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Phenyliodine(III) Dichloride

Knight

Russell

2001

Encyclopedia of Reagents for Organic Synthesis

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Chlorination of cyclopentadiene and 1,3-cyclohexadiene with iodobenzene dichloride and trichloramine

Cited by 14 publications

References 2 publications

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

Phenyliodine(III) Dichloride

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