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I'm having an odd experience with this - a rapid start, with quite a lot much easier than usual with this setter. However I've got several entries I don't fully understand, and I've ground to a halt in the SE. Could I have a hint for this one, please? (I've chosen this as the letters placed are definitely right!)

20 Chap last in Tour: "I don't want any more cycling" (7)
R???H?N
I suspect that "chap" might be a verb form, but I still don't get anything apart from the initial R.

Good morning Chris
the verb to chap is the def
Last letter of tour - R
anagram of a word for "I don't want any more "

Thanks jazzy - I couldn't see the anagram part.
It doesn't help with the crosser, though - any hints
22a Loveless woman of some allure to set about Valentine's rival (6)
T?U???
(I have a tentative 5th letter, but it may well be wrong)

Actually, I haven't fully parsed the clue that gives the T either!

Valentine's rival is the defn
alluring woman 5 letters minus the O inside "to" set about

Valentine"s rival in Two gentlemen of Verona I think

Thanks xwordfan. "Valentine's rival" isn't ringing any bells. Could you give a hint of the context, please?

xwordfan thanks for the parse. I was stuck on that !

You anticipated my request, jazzy - never heard of him. Difficult clue!

Struggling today.
Some help with, Refined tincture in to which is dipped a second pen. 2, 6. *o, *u***r. Thanks