AI Article Synopsis
- The use of affordable, non-toxic transition metals like iron is crucial for sustainable catalytic processes, with iron being the most abundant option available.
- An effective catalyst system composed of FeCl, phenanthroline, and KOBu facilitated the selective sp C-H alkylation of fluorene using environmentally friendly alcohols, producing water as the only byproduct.
- The reaction showed versatility across various substituted fluorenes and benzyl alcohols, maintaining high yields, and demonstrated practical applications through different postfunctionalizations of the resulting products.
Article 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 FeCl (3 mol %), phenanthroline (6 mol %), and KOBu (0.4 eqivalent) was used as an effective catalyst for the sp 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.
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| http://dx.doi.org/10.1021/acs.joc.4c00819 | DOI Listing |
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