Erratum After publication of the original article [1], the authors noticed that one of their correction requests had been missed: In Table 8, column “Prevalence of the barrier”, a superscripted “a” was included next to the “5 %” and “1 %” prevalence data. These “a”s should have been removed. This is now corrected in the original article and also shown in the below table. We apologise for any in...

1. S1. Fictive-Temperature Estimations. 2. Figure S1. MD-Derived Fictive Temperatures. 3. Figure S2. A Selection of Deconvoluted 27Al MAS NMR Spectra. 4. Figure S3. MD-derived Radial Distribution Functions. 5. Figure S4. MD-derived Bond-Angle Distributions. 6. Table S1. MD-Derived Structural Data at Different Melt-Cooling Rates. 7. Table S2. Deconvolution Results of 27Al MAS NMR Spectra Recorde...

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mechanistic pathways: a concerted rearrangement (path a) involving direct addition of the olefin on the epoxide or a stepwise mechanism (path b) through a Nazarov cyclization of an oxypentadienyl cation (2, X=O ). The regioselectivity of the cyclization is dictated by donation of the oxyanion into the resulting cation leading to the formation of a ketone. Recently, stabilization of developing p...