page_title: Cheletropic reaction
section_title: Carbene Additions to Alkenes
hierarchical_section_title: Cheletropic reaction / Carbene Additions to Alkenes
caption_attribution_description: English: scheme of carbene addition to alkene
context_page_description: Cheletropic reactions are a type of pericyclic reaction where one atom on one of the reagents gets two new bonds. A pericyclic reaction is one that involves a transition state with a cyclic array of atoms and an associated cyclic array of interacting orbitals. A reorganization of σ and π bonds occurs in this cyclic array.
  Cheletropic reactions are a subclass of cycloadditions. What sets cheletropic reactions apart is that on one of the reagents, both new bonds are being made to the same atom. A few examples are shown to the right in Figure 1. In the first case, the single atom is the carbon atom in the carbonyl group. That carbon atom ends up in carbon monoxide. The end result is making two new bonds to one atom. The first two examples are known as "cheletropic extrusions" because a small stable molecule is given off in the reaction. The driving force for these reactions is often the entropic benefit of releasing a gas.
context_section_description: One of the most synthetically important cheletropic reactions is the addition of a singlet carbene to an alkene to make a cyclopropane (see figure at left). A carbene is a neutral molecule containing a divalent carbon with six electrons in its valence shell. Because of this, carbenes are highly reactive electrophiles and generated as reaction intermediates. A singlet carbene contains an empty p orbital and a roughly sp² hybrid orbital that has two electrons. Singlet carbenes add stereospecifically to alkenes, and alkene stereochemistry is retained in the cyclopropane product. The mechanism for addition of a carbene to an alkene is a concerted [2+1] cycloaddition (see figure). Carbenes derived from chloroform or bromoform can be used to add CX₂ to an alkene to give a dihalocyclopropane, while the Simmons-Smith reagent adds CH₂.
  Interaction of the filled carbene orbital with the alkene π system creates a four-electron system and favors a non-linear approach. It is also favorable to mix the carbene empty p orbital with the filled alkene π orbital. Favorable mixing occurs through a non-linear approach (see figure 2 at right). However, while theory clearly favors a non-linear approach, there are no obvious experimental implications for a linear vs. non-linear approach.
caption: Addition of a Carbene to an Alkene to Form a Cyclopropane
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