Essentially, you can decoct the mash at any time - it used to be the only way to raise mash temps in wooden mashtuns. Brewers routinely did triple decoctions to give the mash a beta-glucan rest to reduce gumminess in the mash at around 40C, followed by a protein rest at around 53C, then a third decoction to lift the mash into the saccharification range at around 66C. Having a weldless thermometer in the rubbermaid mashtun is a god send!
This table gives you an idea of what's happening at the respective temps:
Kev's process is fine - get the mash up to starch conversion temps, let it rest for 20 mins, pull a third of the grist and boil for 20 mins then return that to the mashtun - obviously that will raise the mash temperture into the "Mashout" temperature range and in another 20 mins you can commence the sparge. The point that Kev also made, which is quite correct, is that conventional wisdom suggests that a decoction done specifically to raise the mash temp to a "mashout" step is to pull a "thin" decoction, ie, plenty of mash liquor and not so much grains from the mashtun.
I have other methods for raising the mash temp - eg, adding boiling water or using the immersion element. So for me, the main reason I do a decoction is to get more melanoidins giving a richer malty flavour profile and slightly darker colour to the final product. Decoctions are very handy and don't dilute the mash...
So if I'm in the mood to decoct, I'll dough-in a stiff mash at 53C at 2L of water per kilo of grains, to give it a protein rest for around 20 mins then pull a thick decoction (usually less than a third of the mash goes into my stovetop pot), boil for 10-20 mins, stirring well, to caramalise sugars (yes, enzymes do convert at 50C), get more melanoidins from the pull and thin the decoction by gelatinising the decoction. I add the boiling decoction and no more than 300ml of boiling water per kilo of grains to lift the mash into the 66C zone and keep the mash thickness / consistency "in the zone" and let the mash rest for an hour at 66C, skip the mashout step and start the sparge when the 1 hour 20 minute mash or glass of beer I'm enjoying has finished!
Cheers,
TL