High Rates of Quinone-Alkyne Cycloaddition Reactions are Dictated by Entropic Factors

13 January 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Reaction rates of strained cycloalkynes and cycloalkenes with 1,2-quinones were quantified by stopped flow UV-Vis spectroscopy. Surprisingly, it was determined that 8-membered BCN-OH reacts substantially (16 times) faster than the more strained 7-membered THS. Thermodynamic activation parameters, obtained from the linearized Eyring equation and stopped-flow measurements, revealed that the reaction of both BCN-OH and THS with ortho-quinones is entropycontrolled, ruling out a relevant contribution of secondary orbital interactions (SOIs) as earlier proposed.


click chemistry
Eyring plot
secondary orbital interactions

Supplementary materials

Supporting Information for High Rates of Quinone-Alkyne Cycloaddition Reactions are Dictated by Entropic Factors
Details on the synthesis and characterization of THS 2 and carbamate derivatives 4 and 6, the setup used for the stopped-flow experiments, data on all kinetic measurements, derivatization of mathematical equations and specifics of the computational studies.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.