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. 2015 Jun;26(6):730-734.
doi: 10.1016/j.cclet.2015.03.016. Epub 2015 Mar 27.

Mechanism and Reactivity of Rh-Catalyzed Intermolecular [5+1] Cycloaddition of 3-Acyloxy-1,4-Enyne (ACE) and CO: A Computational Study

Xiao-Na Ke  1 , Casi M Schienebeck  2 , Chen-Chen Zhou  1 , Xiufang Xu  1 , Weiping Tang  2
Affiliations

Mechanism and Reactivity of Rh-Catalyzed Intermolecular [5+1] Cycloaddition of 3-Acyloxy-1,4-Enyne (ACE) and CO: A Computational Study

Xiao-Na Ke et al. Chin Chem Lett. 2015 Jun.

Abstract

The first theoretical study on the mechanism of [RhCl(CO)2]2-catalyzed [5 + 1] cycloadditions of 3-acyloxy-1,4-enyne (ACE) and CO has been performed using density functional theory (DFT) calculations. The effect of ester on reactivity of this reaction has been investigated. The computational results have revealed that the preferred catalytic cycle involves the sequential steps of 1,2-acyloxy migration, CO insertion, reductive elimination to form ketene intermediate, 6π-electroncyclization, and aromatization to afford the resorcinol product. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity by stabilizing the positive charge building up in the oxocyclic transition state.

Keywords: (5+1) Cycloaddition; DFT; Ester effect; Rhodium catalyst.

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Figures

Figure 1
Figure 1
Gibbs free energy profile of the[RhCl(CO)2]2-catalyzed intermolecular [5 + 1] cycloaddition of ACE 1 and CO. Energies are in kcal/mol and calculated using M06/SDD-6-311+G(d,p)/SMD(CH2Cl2)//B3LYP/SDD-6-31G(d)/SMD(CH2Cl2).
Figure 2
Figure 2
Transition states in pathway a of the [RhCl(CO)2]2-catalyzed intermolecular [5 + 1] cycloaddition of ACE 1 and CO.
Figure 3
Figure 3
NPA charges of transition states entry2-TS1 and entry3-TS1 in Table 1. In the rate-determining 1,2-acyloxy migration step, the ester carbon (C6) is more positively charged in the transition state (TS1) than in the reactant (4) and the product (6). Thus, the electron-rich p-dimethylaminobenzoate substrate stabilizes the positive charge on C6 in the acyloxy migration transition state (entry3-TS1) and promotes the reaction. As expected, the C6 atom in entry3-TS1 is less positively charged than that in the transition state with the acetate substrate (entry2-TS1).
Scheme 1
Scheme 1
[RhCl(CO)2]2-Catalyzed [5+1] Cycloaddition of ACE and CO.
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