image credit: Gemini Observatory/NSF/C.Aspin
Oxygen-16 is a really stable, "doubly-magic" nucleus, in that it contains complete shells of both protons and neutrons. The addition of an alpha particle through fusion with a He nucleus doesn't occur quite so easily for Oxygen-16 as it does for adding an alpha particle to Neon-20.
In fact "oxygen-burning" occurs most readily by combining an oxygen nucleus with another oxygen nucleus, partly I guess because the He nuclei get vacuumed up by reactions with carbon and neon first. As a result, the Coulomb barrier is much higher for oxygen-burning and it needs high temperatures than neon-burning. Thus the oxygen-burning and neon-burning shells appear "out of order" compared with how you might think they would be.