Vocabulary

antarafacial

describes when one π\pi system must twist to align like phases of the p orbitals so that two bonding interactions will occur

Claisen rearrangement

[3,3]-sigmatropic rearrangement that involves the rearrangement of vinyl allyl ethers (phenyl allyl ethers) to unsaturated carbonyls

conjugated diene

diene with two double bonds that are separated by one single bond

conrotatory

classification that describes when the two ends of the polyalkene rotate in the same direction during the movement of the molecular orbital to form new σ\sigma bonds in the cyclization reaction

Cope rearrangement

[3,3]-sigmatropic rearrangement that involves the rearrangement of 1,5-dienes to a regioisomer, an isomer based on the location of a functional group

cumulated diene

diene with two successive double bonds without an intervening single bond

cycloaddition reaction

concerted reaction in which two or more unsaturated molecules (or parts of the same molecule) combine to form a cyclic product, with a net reduction of bond multiplicity

Diels-Alder reaction

concerted reaction in which two new σ\sigma bonds are formed at the expense of two π\pi bonds of the conjugated diene and dienophile

diene

compound containing two double bonds (or a 4 π\pi-electron system)

dienophile

compound containing a double bond (or a two π\pi-electron system)

disrotatory

classification that describes when the two ends of the polyalkene rotate in opposite directions during the movement of the molecular orbital to form new σ\sigma bonds in the cyclization reaction

electrocyclic reaction

reversible reaction that involves ring closure of a conjugated polyalkene to a cycloalkene or ring opening of a cycloalkene to a conjugated polyalkene

electrophilic addition

reaction of a double (or triple) bond with an electrophile to give a carbocation (or another cationic intermediate) that then reacts with a nucleophile. The reaction breaks a π\pi-bond and a σ\sigma-bond while simultaneously creating two σ\sigma-bonds.

endo rule

stereochemical preference for the electron-withdrawing substituent to appear in the endo position rather than the exo position

frontier molecular orbital theory

concept that the highest-energy occupied orbitals of one molecule interact with the highest-energy unoccupied orbitals of another molecule

highest occupied molecular orbital (HOMO)

highest energy level that is occupied by electrons

isolated diene

diene with two double bonds separated by two or more single bonds

kinetic control

situation in which the reaction to form products is irreversible and the product ratio is determined by the reaction rate

lowest unoccupied molecular orbital (LUMO)

lowest energy level that is not occupied by electrons

pericyclic reaction

reaction in which bonds are made or broken in a concerted cyclic transition state

photochemical change

chemical change initiated by light

regioselectivity

preference of one direction of chemical bond making or breaking over all other possible directions

sigmatropic reaction

reaction in which the net result is that one σ\sigma bond is changed to another σ\sigma bond in an uncatalyzed intramolecular process

suprafacial

having like phases of the p orbitals of two molecules on the same side of the π\pi systems so that two bonding interactions occur

thermal condition

condition of a reaction where heat is the deciding factor in the distribution of products

thermodynamic control

situation in which the reaction to form products is reversible and the product ratio is determined by relative thermodynamic stabilities

Woodward-Hoffmann rules

set of rules used to rationalize or predict certain aspects of the stereochemical outcome and activation energy of pericyclic reactions