Deprotonative Metalation Using Ate Compounds: Synergy, Synthesis, and Structure Building

Historically, single‐metal organometallic species such as organolithium compounds have been the reagents of choice in synthetic organic chemistry for performing deprotonation reactions. Over the past few years, a complementary new class of metalating agents has started to emerge. Owing to a variable central metal (magnesium, zinc, or aluminum), variable ligands (both in their nature and number), and a variable second metallic center (an alkali metal such as lithium or sodium), “ate” complexes are highly versatile bases that exhibit a synergic chemistry which cannot be replicated by the homometallic magnesium, zinc, or aluminum compounds on their own. Deprotonation accomplished by using these organometallic ate complexes has opened up new perspectives in organic chemistry with unprecedented reactivities and sometimes unusual and unpredictable regioselectivities. Crazy ates: Metalations of organic substrates with alkali‐metal magnesiates, zincates, and aluminates have opened up new perspectives in synthetic and structural chemistry. This Review covers selected syntheses made possible by application of such “ate” complexes as deprotonation reagents, together with insight into synergetic effects in the syntheses of these species.