Manganese-Catalyzed Dehydrogenative/Deoxygenative Coupling of Alcohols

Abstract

Valorization of biomass has become an area of intense focus because of the diminishing reserves of crude oil and the ongoing problem of climate change. The principal strategies for the utilization of biomass as a feedstock are (i) to produce biofuels for the transportation sector and (ii) to produce organic commodity chemicals. In this respect, we have developed a serious of manganese-catalyzed dehydrogenative/deoxygenative coupling reactions of lower alcohols, obtainable from oxygen-rich lignocellulosic biomass, to deliver advanced liquid fuels and valuable chemicals.1 Introduction2 Manganese-Catalyzed Upgrading of Ethanol to Butan-1-ol3 Manganese-Catalyzed Selective Upgrading of Ethanol with Methanol to Isobutanol4 Manganese-Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols with Hydroxides to Give Carboxylates5 Manganese-Catalyzed Dual-Deoxygenative Coupling of Primary Alcohols with 2-Arylethanols6 Conclusion

NNN Pincer-Manganese-Catalyzed Guerbet-Type β-Alkylation of Alcohols under Microwave Irradiation

“…Accordingly, the early transition metals, such as iron, cobalt, nickel, and chromium, have recently gained much attention for the β-alkylation reactions. Manganese, which ranks third in terms of abundance, has proven to be an exciting alternative to noble metals in the past few years for several reactions where alcohols have been used as alkylating agents . In the context of the current work, it is noteworthy that the β- alkylation of secondary alcohols using primary alcohols by a Mn-based catalyst was first reported by Yu and co-workers, where they have obtained 92% of the β-alkylated product using 2.1 mol % of a bidentate Mn catalyst in the presence of KO t Bu (30 mol %) at 135 °C.…”

Manganese/bipyridine-catalyzed non-directed C(sp3)–H bromination using NBS and TMSN3

“…Manganese is one of the most abundant and nontoxic transition metals found in the earth's crust and its corresponding complexes and salts are useful in synthetic organic reactions [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43]. Highly reactive and selective bromination reactions have been achieved using a stoichiometric amount of MnO 2 [44] or a catalytic amount of Li 2 MnO 3 [45] under fluorescent light irradiation in the presence of Br 2 (Scheme 1d).…”