Mechanism Study Of Cu-catalyzed Ring Opening Reaction Of Benzocyclobutanol

The carbon-carbon bond is the basic framework for the formation of organic compounds.Its selection of reaction position and activation of fault are the basis of cyclic compound's ring-opening reaction and the functionalization after bond-broken,and are significant to the process study of organic chemical reactions and synthetic application in laboratory.Benzocyclobutenol is very often the building block of composing complex structural cyclic molecules and natural products.A study into its selective reaction of C?sp³?-C?sp³?bond breaking and C?sp²?-C?sp³?bond breaking is an field of great research value.In recent years,more attention is paid to the carbon-carbon bond breaking in copper catalytic reaction.Because copper has the characteristics of being low-priced and low-toxic as a catalyzer,it is often used to catalyze the carbon-carbon bond.Howover,since the study into its mechanism of catalyzing is still incomplete,it has the practical significance to explore the mechanism of this reaction.This article adopted Density Functional Theory to study the reaction mechanism of the carbon-carbon bond breaking catalyzed by [Cu?OH??cod?]₂.The study found the reaction mechanism includes three steps.The first step is the formation of an intermediate through benzocyclobutenol's deprotonation.The second step is the?-carbon elimination of carbon-carbon bond breaking.The third step is the proton transfer process of H₂ O,making reaction products,and the reformation of catalyzers.In the key step of the ?-carbon elimination,it's found that the hydrone transferred in the proton transfer process could be eliminated and also can participate in the carbon-carbon breaking reaction.The study also found that C?sp²?-C?sp³?bond breaking is much easier compared to C?sp³?-C(sp³ breaking in the reaction process.In addition,the study found that the optimum route of the carbon-carbon bond breaking is RCma ? TSR0 ma ? M0 ma ?TS12a_w?sp³?? IM2a-w where the hydrone exists in C?sp²?-C?sp³?bond breaking process but not coordinate with[Cu?OH??cod?]₂.