Stereochemical Investigations Reveal the Mechanism of the Bacterial Activation of n‐Alkanes without Oxygen

Anaerobic growth of the bacterium strain HxN1 with n-hexane gives nearly equal amounts of (2R,1′R)- and (2S,1′R)-(1-methylpentyl)succinate, which are formed by the radical addition of the hydrocarbon to fumarate (see scheme). The highly selective attack on the pro-S hydrogen atom at C2 of n-hexane is associated with inversion of the configuration at C2 during binding to fumarate and exhibits isotopic discrimination against a C2H bond.