Figure 5: Free-energy profiles for the two competing mechanisms. | Nature Communications

Figure 5: Free-energy profiles for the two competing mechanisms.

From: Towards a general diastereoselective route to oxabicyclo[3.2.1]octanes via a gold-catalysed cascade reaction

Figure 5

(a) SMD-M11-L/6-311+G(d)//B3LYP/6-31+G(d) (SDD for Au) calculated free-energy profile for the sequence of intramolecular nucleophilic addition/semi-pinacol rearrangement of 1-ethynylcyclohexane-trans-1,4-diols established in this study for the reaction of key intermediate CP1. This indicates that the semi-pinacol rearrangement is the rate-determining step of this reaction and formation of complex 10 via transition state TS5 is both thermodynamically and kinetically favourable (see Supplementary Tables 1 and 2). (b) The Newman projections of transition states TS5 and TS6.

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