The manganese-mediated regioselective chlorination of allenes in synthetic approaches towards the spongistatins and halomon natural products

Boyes, Alastair L.; Wild, Mark

doi:10.1016/s0040-4039(98)01410-5

Cited by 26 publications

(8 citation statements)

References 17 publications

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“…187 The use of BnNEt 3 MnO 4 with (COCl) 2 or Me 3 SiCl as promoters has also been extended to the vicinal dichlorination of allenes. 188 …”

Section: Alkene Dihalogenations With Transition Metal Halides As Rmentioning

confidence: 99%

“…[187] Theu se of BnNEt 3 MnO 4 with (COCl) 2 or Me 3 SiCl as promoters has also been extended to the vicinal dichlorination of allenes. [188] Markó et al have suggested that chloriranium ions (arising either from molecular Cl 2 or some other Cl + equivalent) are unlikely to be intermediates in these manganese(VII)-mediated dichlorinations.S pecifically,d ifferent product distributions are observed for the dichlorination of cyclooctadiene monoepoxide 77 with either Cl 2 (in CH 2 Cl 2 at 20 8 8C) or Markós reagent [using either (COCl) 2 at À40 8 8C [32b] or Me 3 SiCl at 0!20 8 8C.…”

Section: Angewandte Reviewsmentioning

confidence: 99%

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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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“…187 The use of BnNEt 3 MnO 4 with (COCl) 2 or Me 3 SiCl as promoters has also been extended to the vicinal dichlorination of allenes. 188 …”

Section: Alkene Dihalogenations With Transition Metal Halides As Rmentioning

confidence: 99%

Section: Angewandte Reviewsmentioning

confidence: 99%

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

2015

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“…Although the cyclic allene 59 afforded one major product 60 with 92% yield, the terminal allenes 61 yielded the three regioisomers 62–64 in varying ratios (Scheme ). As a result, the use of oxalyl chloride as the chlorine donor in the MnCl 2 reagent is not effective for the regioselective chlorination of terminal allenes …”

Section: Chlorinationmentioning

confidence: 99%

Oxalyl Chloride: A Versatile Reagent in Organic Transformations

Mohammadkhani

Heravi

2019

ChemistrySelect

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Oxalyl chloride, (COCl)2, as an inexpensive commercially available chemical is one of the most versatile applicable organic reagents in chemical transformations. It is also employed extensively in various chemical industries. It is employed in various chemical transformations such as chlorination, oxidation, reduction, dehydration, decarboxylation, and formylation reactions as well as ring cleavage of epoxides. During the past decades, numerous procedures using (COCl)2 as reagent have been developed and published. However, its importance has largely been overlooked by the absence of a comprehensive review in chemical literature dealing with its application in organic transformations and its utilization in the chemical industry. This Review aims to provide an overview for the applications of oxalyl chloride in organic synthesis, including its physical properties, synthesis, as well as its unique roles as the reagent in organic reactions, covering the literature over the past 103 years (from 1916 to date).

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“…Thus, the development of strategies for their synthesis is an important endeavour. We envisioned accomplishing this by developing a chemo- and regioselective vicinal -dichlorination of phenylallenes; however, no such chlorination reaction has yet been achieved [29–34]. …”

Section: Introductionmentioning

confidence: 99%

Chlorination of phenylallene derivatives with 1-chloro-1,2-benziodoxol-3-one: synthesis of vicinal-dichlorides and chlorodienes

Zhao¹,

Murphy²

2018

Beilstein J. Org. Chem.

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Allyl and vinyl chlorides represent important structural motifs in organic chemistry. Herein is described the chemoselective and regioselective reaction of aryl- and α-substituted phenylallenes with the hypervalent iodine (HVI) reagent 1-chloro-1,2-benziodoxol-3-one. The reaction typically results in vicinal dichlorides, except with proton-containing α-alkyl substituents, which instead give chlorinated dienes as the major product. Experimental evidence suggests that a radical mechanism is involved.

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The manganese-mediated regioselective chlorination of allenes in synthetic approaches towards the spongistatins and halomon natural products

Cited by 26 publications

References 17 publications

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Oxalyl Chloride: A Versatile Reagent in Organic Transformations

Chlorination of phenylallene derivatives with 1-chloro-1,2-benziodoxol-3-one: synthesis of vicinal-dichlorides and chlorodienes

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