Selective Terminal Functionalization of Linear Alkanes

A two‐step sequential strategy involving a biocatalytic dehydrogenation/remote hydrofunctionalization, as a unified and versatile approach to selectively convert linear alkanes into a large array of valuable functionalized aliphatic derivatives is reported. The dehydrogenation is carried out by a mutant strain of a bacteria Rhodococcus and the produced alkenes are subsequently engaged in a remote functionalization through a metal‐catalyzed hydrometalation/migration sequence that subsequently react with a large variety of electrophiles. The judicious implementation of this combined biocatalytic and organometallic approach enabled us to develop a high‐yielding protocol to site‐selectively functionalize unreactive primary C−H bonds. A two‐step sequential strategy, involving a biocatalytic dehydrogenation/remote hydrofunctionalization as a unified and versatile approach to selectively convert linear alkanes into a large array of valuable functionalized aliphatic derivatives is reported. The reaction goes through a site‐selective functionalization at the unreactive primary C−H bonds of the linear alkane and avoids the use of linear α‐olefins.