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Halogenation of Alkenes02:46

Halogenation of Alkenes

15.6K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
15.6K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

14.1K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
14.1K
Carbocations02:10

Carbocations

11.2K
Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
11.2K
Reactions of α-Halocarbonyl Compounds: Nucleophilic Substitution01:17

Reactions of α-Halocarbonyl Compounds: Nucleophilic Substitution

3.2K
Nucleophilic substitution in α-halocarbonyl compounds can be achieved via an SN2 pathway. The reaction in α-haloketones is generally carried out with less basic nucleophiles. The use of strong basic nucleophiles leads to the generation of α-haloenolate ions, which often participate in other side reactions.
3.2K
Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

4.0K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.0K
Base-Promoted α-Halogenation of Aldehydes and Ketones00:51

Base-Promoted α-Halogenation of Aldehydes and Ketones

3.4K
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base.  The reaction begins with the abstraction of  α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
3.4K

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Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
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Stereoselective Nucleophilic Halogenation at CF3-Substituted Nonclassical Carbocation.

Veronika Myronova1,2, Dominique Cahard2, Ilan Marek1

  • 1The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and the Resnick Sustainability Center for Catalysis. Technion-Israel Institute of Technology, Haifa 3200009, Israel.

Organic Letters
|April 24, 2024
PubMed
Summary

Trifluoromethyl-substituted cyclopropyl carbinols yield single diastereomer acyclic products via regioselective halogenation. This reaction proceeds through a unique cyclopropylcarbinyl cation intermediate, enabling efficient synthesis of chiral fluorinated compounds.

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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
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Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
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Area of Science:

  • Organic Chemistry
  • Fluorine Chemistry
  • Stereoselective Synthesis

Background:

  • Trifluoromethyl (CF3)-substituted cyclopropyl carbinol derivatives present unique synthetic challenges.
  • Controlling regioselectivity and diastereoselectivity in reactions involving strained ring systems is crucial for developing novel chiral molecules.

Purpose of the Study:

  • To investigate the regioselective and diastereoselective nucleophilic halogenation of CF3-substituted cyclopropyl carbinol derivatives.
  • To elucidate the reaction mechanism and rationalize the observed stereochemical outcome.
  • To develop an efficient catalytic method for synthesizing stereochemically pure acyclic halogenated compounds.

Main Methods:

  • Nucleophilic halogenation reactions on CF3-substituted cyclopropyl carbinols.
  • Analysis of reaction products using stereochemical analysis techniques.
  • Computational studies to support the proposed reaction mechanism involving nonclassical carbocation intermediates.

Main Results:

  • Regioselective and diastereoselective halogenation occurred exclusively at the quaternary carbon center.
  • Acyclic products were obtained as single diastereomers.
  • The reaction pathway was rationalized by the formation of a nonclassical cyclopropylcarbinyl cation intermediate.
  • Tertiary alkyl chlorides, bromides, and fluorides adjacent to a stereogenic C-CF3-motif were synthesized with high diastereomeric purity.

Conclusions:

  • The developed method provides efficient access to diastereomerically pure acyclic halogenated compounds bearing a CF3-motif.
  • The reaction proceeds via a unique nonclassical cyclopropylcarbinyl cation intermediate, highlighting novel reactivity patterns.
  • This approach offers a valuable synthetic route from readily available alkynes to complex chiral fluorinated molecules.