ChemInform Abstract: Halonium‐Induced Cyclization Reactions

Snyder, Scott A.; Treitler, Daniel S.; Brucks, Alexandria P.

doi:10.1002/chin.201205253

Cited by 38 publications

(52 citation statements)

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“…4f In this way, an uncatalyzed background reaction of the alkene with the halogenating agent can be minimized. Another distinct strategy is phase transfer catalysis, in which the alkene substrate and reactive halogenating agent are physically separated in different phases until brought into contact by the catalyst.…”

Section: Challenges For Stereoselective Catalysismentioning

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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Section: Challenges For Stereoselective Catalysismentioning

confidence: 99%

“…Whilst the field is undoubtedly still in its infancy, a variety of catalytic, enantioselective olefin difunctionalization reactions involving all four (common) halogens have now been realized, and these transformations fall under the broad umbrella of “alkene halofunctionalization” reactions. 4 …”

Section: Introduction: State Of the Artmentioning

confidence: 99%

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

2015

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“…1 Consequently, the development of asymmetric variants of halolactonization reactions has received considerable attention in recent years, and some significant advances have been made. 2 We recently reported the discovery of the bifunctional organic catalyst 1 that promotes highly efficient enantioselective halolactonization reactions for a broad array of olefinic acids (Equation 1).…”

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confidence: 99%

Synthesis of (+)-Disparlure via Enantioselective Iodolactonization

Klosowski

Martin

2018

Org. Lett.

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The BINOL-amidine organic catalyst 1 was previously shown to promote highly efficient enantioselective halolactonization reactions of olefinic acids. As part of these studies, it was discovered that the enantioenriched iodolactones could be easily converted into enantioenriched cis-1,2-disubstituted epoxides. This halolactonization-epoxidation sequence was applied to the synthesis of (+)-disparlure, which resulted in the shortest catalytic enantioselective synthesis to date, requiring only five steps and proceeding in 33% yield.

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“…As sources of electrophilic halogens, they are applicable for I + or Br + transfer reactions, in, for example, the halogenation of alkenes, alkynes, and aromatics, in oxidations, and in halocyclizations [76,90,91]. The earliest [bis (pyridine)iodine] + and [bis(pyridine)bromine] + complexes were generated in situ from chloroform solutions of pyridine and AgNO 3 upon addition of Br 2 [92] or INO 3 [93].…”

Section: Charged Three-center Halogen Bond Complexesmentioning

confidence: 99%

Halogen Bonding in Solution

Carlsson

Veiga

Erdélyi

2014

Topics in Current Chemistry

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Because of its expected applicability for modulation of molecular recognition phenomena in chemistry and biology, halogen bonding has lately attracted rapidly increasing interest. As most of these processes proceed in solution, the understanding of the influence of solvents on the interaction is of utmost importance. In addition, solution studies provide fundamental insights into the nature of halogen bonding, including, for example, the relative importance of charge transfer, dispersion, and electrostatics forces. Herein, a selection of halogen bonding literature is reviewed with the discussion focusing on the solvent effect and the electronic characteristics of halogen bonded complexes. Hence, charged and neutral systems together with two- and three-center bonds are presented in separate sub-sections. Solvent polarity is shown to have a slight stabilizing effect on neutral, two-center halogen bonds while strongly destabilizes charged, two-center complexes. It does not greatly influence the geometry of three-center halogen bonds, even though polar solvents facilitate dissociation of the counter-ion of charged three-center bonds. The charged three-center bonds are strengthened by increased environment polarity. Solvents possessing hydrogen bond donor functionalities efficiently destabilize all types of halogen bonds, primarily because of halogen vs hydrogen bond competition. A purely electrostatic model is insufficient for the description of halogen bonds in polar systems whereas it may give reasonable correlation to experimental data obtained in noninteracting, apolar solvents. Whereas dispersion plays a significant role for neutral, two-center halogen bonds, charged halogen bond complexes possess a significant charge transfer characteristic.

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ChemInform Abstract: Halonium‐Induced Cyclization Reactions

Abstract: Review: 165 refs.

Cited by 38 publications

References 0 publications

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Synthesis of (+)-Disparlure via Enantioselective Iodolactonization

Halogen Bonding in Solution

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