烯丙位张力 (也被称为1,3-烯丙位张力).docVIP

Allylic strain (also known as A1,3 strain, 1,3-allylic strain, or A-strain) in HYPERLINK /wiki/Organic_chemistry \o Organic chemistry organic chemistry is a type of HYPERLINK /wiki/Strain_energy \o Strain energy strain energy resulting from the interaction between a substituent on one end of an olefin with an allylic substituent on the other end. HYPERLINK /wiki/Allylic_strain \l cite_note-AD-Book-1#cite_note-AD-Book-1 [1] If the substituents (R and R) are large enough in size, they can sterically interfere with each other such that one HYPERLINK /wiki/Conformational_isomerism \o Conformational isomerism conformer is greatly favored over the other. HYPERLINK /wiki/Allylic_strain \l cite_note-J1968-2#cite_note-J1968-2 [2] Allyic strain was first recognized in the literature in 1965 by Johnson and Malhotra. The authors were investigating cyclohexane conformations including endocyclic and exocylic double bonds when they noticed certain conformations were disfavored due to the geometry constraints caused by the double bond. HYPERLINK /wiki/Allylic_strain \l cite_note-JM1965-3#cite_note-JM1965-3 [3] Organic chemists capitalize on the rigidity resulting from allylic strain for use in asymmetric reactions. HYPERLINK /wiki/Allylic_strain \l cite_note-J1968-2#cite_note-J1968-2 [2] HYPERLINK /wiki/File:Generic_allylic_strain.png \o Enlarge Allylic strain in an olefin. Quantifying Allylic Strain Energy The strain energy of a molecule is a quantity that is difficult to precisely define, so the meaning of this term can easily vary depending on ones interpretation. HYPERLINK /wiki/Allylic_strain \l cite_note-Allinger-4#cite_note-Allinger-4 [4] Instead, an objective way to view the allylic strain of a molecule is through its conformational equilibrium. Comparing the heats of formation of the involved conformers, an overall ΔHeq can be evaluated. This term gives information about the relative stabilities of the involved conformers and the effect allylic strain has on equilibr