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

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 a hydrogen auto-transfer methodology. The sole by-product formed is water, rendering the protocol atom efficient. Electronic structure theory studies corroborated the proposed mechanism.

Advances in Group VI Metal-Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions.

Transition metal-catalyzed homogeneous hydrogenation and dehydrogenation reactions for attaining plethora of organic scaffolds have evolved as a key domain of research in academia and industry. These protocols are atom-economic, greener, in line with the goal of sustainability, eventually pave the way for numerous novel environmentally benign methodologies. Appealing progress has been achieved in the realm of homogeneous catalysis utilizing noble metals. Owing to their high cost, less abundance along with toxicity issues led the scientific community to search for sustainable alternatives. In this context, earth- abundant base metals have gained substantial attention culminating enormous progress in recent years, predominantly with pincer-type complexes of nickel, cobalt, iron, and manganese. In this regard, group VI chromium, molybdenum and tungsten complexes have been overlooked and remain underdeveloped despite their earth-abundance and bio-compatibility. This review delineates a comprehensive overview in the arena of homogeneously catalysed (de)hydrogenation reactions using group VI base metals chromium, molybdenum, and tungsten till date. Various reactions have been described; hydrogenation, transfer hydrogenation, dehydrogenation, acceptorless dehydrogenative coupling, hydrogen auto transfer, along with their scope and brief mechanistic insights.