Like CO, isocyanides (:CNR) are ambiphilic ligands with σdonor and π-acceptor properties, which have been widely used in transition metal chemistry. We began our investigations with alkyl isocyanides and metalated ylide 1 as model substrates. Unfortunately, treatment of in-situ generated 1 with tert-butyl isocyanide resulted in no reaction to the targeted keteniminyl anion 3e, even when the reaction was conducted at elevated temperatures (Scheme 1). However, when using cyclohexyl isocyanide selective release of PPh3 (δP = -5.42 ppm) was observed as confirmed by P{ 1 H} NMR spectroscopy, indicating a Scheme 1. Synthetic routes to keteniminyl anions 3.