NNN manganese complex-catalyzed α-alkylation of methyl ketones using alcohols: an experimental and computational study

Abstract

We present here a phosphine-free, quinoline-based pincer Mn catalyst for α-alkylation of methyl ketones using primary alcohols as alkyl surrogates. The C-C bond formation reaction proceeds via hydrogen auto transfer...

Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

“…Very recently, a quinoline-based manganese catalyst was studied by Chakraborty and co-workers for the alkylation of methyl aryl ketones with alcohols ( Scheme 41 ) [ 70 ]. Several methyl ketones and alcohols were studied using 2.5 mol % of Mn16 and 30 mol % of NaOH in toluene and yields up to 90% were achieved at high temperature (150 °C) and long reaction time (48 h).…”

Ruthenium Complexes with NNN-Pincer Ligands for N-Methylation of Amines Using Methanol

“…The development of practical and eco-compatible conditions for the synthesis of target chemical molecules is highly desirable in both inorganic and organic synthesis . Borrowing hydrogen (BH) is one of the preeminent strategies in synthesizing high-value-added molecules from cheap and abundant alcohols, releasing H 2 O as the sole byproduct. − Although significant progress has been made using primary and secondary aromatic alcohols as alkylating agents, , the activation of aliphatic alcohols, especially methanol, is more challenging due to its higher dehydrogenation energy barrier (Δ H = 84 kJ/mol) . Thus, high temperature and long reaction time are usually required for efficient conversion in C-methylation and N-methylation reactions.…”

Quinoline-derived NNP-manganese complex catalyzed α-alkylation of ketones with primary alcohols

“…8 Soon afterwards, several other pincer phosphine-based Mn complexes have been applied to similar reactions by the groups of Milstein, 9 Gunanathan, 10 Sortais, 11 a Rueping, 11 b Ruiter 11 c and others. 7 In addition, phosphine-free N- and carbine-based catalytic systems have been developed recently for alkylation reactions by the groups of Maji, 12 Ke, 13 and Chakraborty 14 (Fig. 1).…”