Presented　herein　is　a　series　of　C–X　(X　​=　​O,　S)　couplings　for　the　synthesis　of　esters　and　thioethers　via　difluorocarbene-promoted　selective　Csp3–N　bond　cleavage　between　tertiary　amines　and　carboxylic　acids　or　thiols.　In　those　reactions,　difluorocarbene　plays　an　important　role　for　generating　quaternary　ammonium　salts　and　thus　efficiently　activates　the　Csp3–N　bonds　in　aliphatic　tertiary　acyclic　amines.　The　developed　reaction　does　not　require　any　transition　metal　catalyst　and　features　broad　substrate　scope,　good　functional　group　compatibility　and　ease　of　execution　with　more　than　70　examples　in　total.　©　2024　Fudan　University