Saruman the White

Ward {2}
Whenever you cast your second spell each turn, amass Orcs 2. (Put two +1/+1 counters on an Army you control. It's also an Orc. If you don't control an Army, create a 0/0 black Orc Army creature token first.)

The Council of Four

Whenever a player draws their second card during their turn, you draw a card.
Whenever a player casts their second spell during their turn, you create a 2/2 white Knight creature token.

Tomb of Horrors Adventurer

When Tomb of Horrors Adventurer enters the battlefield, you take the initiative.
Whenever you cast your second spell each turn, copy it. If you've completed a dungeon, copy that spell twice instead. You may choose new targets for the copies. (A copy of a permanent spell becomes a token.)

Rammas Echor, Ancient Shield

Whenever you cast your second spell each turn, draw a card, then create a 0/3 white Wall creature token with defender.
At the beginning of combat on your turn, creatures you control with defender gain exalted until end of turn. (Whenever a creature you control attacks alone, it gets +1/+1 until end of turn for each instance of exalted among permanents you control.)

Saruman of Many Colors

Ward—Discard an enchantment, instant, or sorcery card.
Whenever you cast your second spell each turn, each opponent mills two cards. When one or more cards are milled this way, exile target enchantment, instant, or sorcery card with equal or lesser mana value than that spell from an opponent's graveyard. Copy the exiled card. You may cast the copy without paying its mana cost.

Storm of Saruman

Ward {3}
Whenever you cast your second spell each turn, copy it, except the copy isn't legendary. You may choose new targets for the copy. (A copy of a permanent spell becomes a token.)

Lotho, Corrupt Shirriff

Whenever a player casts their second spell each turn, you lose 1 life and create a Treasure token. (It's an artifact with "{T}, Sacrifice this artifact: Add one mana of any color.")

Copy Enchantment

You may have Copy Enchantment enter the battlefield as a copy of any enchantment on the battlefield.

Ledger Shredder

Flying
Whenever a player casts their second spell each turn, Ledger Shredder connives. (Draw a card, then discard a card. If you discarded a nonland card, put a +1/+1 counter on this creature.)

Firja, Judge of Valor

Flying, lifelink
Whenever you cast your second spell each turn, look at the top three cards of your library. Put one of them into your hand and the rest into your graveyard.