The formation of the structurally novel, mono-substituted cycloheptane ring in ω-cycloheptyl fatty acids in Alicyclobacillus cycloheptanicus (formerly Bacillus cycloheptanicus) has been examined. Feeding experiments with 13C-and 2H-labeled intermediates demonstrated that cycloheptanecarboxylic acid (3), probably as its CoA thioester, is the starter unit for ω- cycloheptyl fatty acid biosynthesis. Analysis of the resultant labeling pattern from a feeding ...