Iron-Catalyzed sp3 C-H Alkylation of Fluorene with Primary and Secondary Alcohols: A Borrowing Hydrogen Approach.

Abstract

The utilization of earth-abundant, cheap, and nontoxic transition metals in important catalytic transformations is essential for sustainable development, and iron has gained significant attention as the most abundant transition metal. A mixture of FeCl₂ (3 mol %), phenanthroline (6 mol %), and KOtBu (0.4 eqivalent) was used as an effective catalyst for the sp³ C-H alkylation of fluorene using alcohol as a nonhazardous alkylating partner, and eco-friendly water was formed as the only byproduct. The substrate scope includes a wide range of substituted fluorenes and substituted benzyl alcohols. The reaction is equally effective with challenging secondary alcohols and unactivated aliphatic alcohols. Selective mono-C9-alkylation of fluorenes with alcohols yielded the corresponding products in good isolated yields. Various postfunctionalizations of C-9 alkylated fluorene products were performed to establish the practical utility of this catalytic alkylation. Control experiments suggested a homogeneous reaction path involving borrowing hydrogen mechanism with the formation and subsequent reduction of 9-alkylidene fluorene intermediate.