Check your textbook. There is likely a section in the Diels-Alder reaction itself and if there is, there will be a portion about how electron withdrawing and donating groups effect the reactivity of the diene and dieneophile.
Although, if you know which - the diene or the dieneophile - is the nucleophile and electrophile you could work it out yourself.
For the second question, an Sn1 requires a carbocation intermediate. Which of those compounds could form the most stable intermediate?