Go off with naked canoeist? (5)
I believe the answer is:
addle
'go off' is the definition.
(eg an egg might addle)
'naked canoeist?' is the wordplay.
'naked' says to take the centre.
'canoeist?' becomes 'paddler' ('paddler' can be a synonym of 'canoeist').
The central letters of 'paddler' are 'ADDLE'.
'with' acts as a link.
(Other definitions for addle that I've seen before include "confusing" , "Get confused" , "Make rotten" , "Rot" , "Confuse - decay" .)