Abstract The generation of higher order and “non-ate” allyl organocopper reagents have been achieved through the low temperature reaction of allyl chlorides with a formal copper anion. The copper anion is generated via the low temperature reduction of Cu (I) complexes by two equivalents of lithium naphthalenide and then oxidatively adds to allyl chlorides with minimal homocoupling. These allyl organocopper reagents undergo substitution reactions ...