Lithium dicyclohexylamide (Cy2NLi) reacts with syn-gas or CO to generate transient intermediates with carbene character, which are capable of reacting further with CO or H-2, effecting sequential C-C and C-H bond formations from CO or H-2, thus providing a transition-metal-free avenue to the fundamental reactions of the Fischer-Tropsch process. Further experimental and computational data indicate that reactions with CO and H-2 are thermodynamically accessible, with a kinetic bias toward CO homologation.