Sustainable and Affordable Synthesis of (Deuterated) N-Methyl/Ethyl Amines from Nitroarenes.

The sustainable and affordable synthesis of (deuterated) N-methyl/ethyl amines directly from nitroarenes is disclosed. The reaction is catalyzed by a single-site manganese catalyst and involves tandem dehydrogenation, transfer hydrogenation, and borrowing hydrogenation. This catalytic protocol is highly selective and provides a facile method for the large-scale synthesis of a series of N-CH3/N-CD3 aniline derivatives with excellent functional group tolerance.

First-Row Transition-Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account.

The development of sustainable catalytic protocols that circumvent the use of expensive and precious metal catalysts and avoid toxic reagents plays a crucial role in organic synthesis. Indeed, the direct employment of simple and abundantly available feedstock chemicals as the starting materials broadens their synthetic application in contemporary research. In particular, the transition metal-catalyzed diversification of alcohols with various nucleophilic partners to construct a wide range of building blocks is a powerful and highly desirable methodology. Moreover, the replacement of precious metal catalysts by non-precious and less toxic metals for selective transformations is one of the main goals and has been paid significant attention to in modern chemistry. In view of this, the first-row transition metal catalysts find extensive applications in various synthetic transformations such as catalytic hydrogenation, dehydrogenation, and related reactions. Herein, we have disclosed our recent developments on the base-metal catalysis such as Mn, Fe, Co, and Ni for the acceptorless dehydrogenation reactions and its application in the C-C and C-N bond formation via hydrogen auto-transfer (HA) and acceptorless dehydrogenation coupling (ADC) reactions. These HA/ADC protocols employ alcohol as alkylating agents and eliminate water and/or hydrogen gas as by-products, representing highly atom-efficient and environmentally benign reactions. Furthermore, diverse simple to complex organic molecules synthesis by C-C and C-N bond formation using feedstock alcohols are also overviewed. Overall, this account deals with the contribution and development of efficient and novel homogeneous as well as heterogeneous base-metal catalysts for sustainable chemical synthesis.

Convenient semihydrogenation of azoarenes to hydrazoarenes using H2.

The high atom-economical and eco-benign nature of hydrogenation reactions make them much more superior to conventional reduction and transfer hydrogenation. Herein, a convenient and highly selective hydrogenation reaction of azoarenes using molecular hydrogen to access diverse hydrazoarenes is reported. The present catalytic method is general and operationally simple, and it operates under exceedingly mild conditions (room temperature and 1 atm of hydrogen pressure). The reusability of catalysts used in this method is also successfully demonstrated.

Recent advances in nickel-catalyzed C-C and C-N bond formation via HA and ADC reactions.

In recent times, earth-abundant 3d-transition-metal catalysts have attracted much attention in contemporary catalysis. They have been widely employed as suitable alternatives to their counterparts noble metals. In particular, nickel catalysts provide distinctive redox properties; thus, their efficiency in sustainable organic transformations is manifold. In this review article, recent advances in nickel-catalyzed hydrogen auto-transfer (HA) and acceptorless dehydrogenative coupling (ADC) reactions for the construction of C-C and C-N bonds have been discussed.

Selective hydrogenation of primary amides and cyclic di-peptides under Ru-catalysis.

A ruthenium(ii)-catalyzed selective hydrogenation of challenging primary amides and cyclic di-peptides to their corresponding primary alcohols and amino alcohols, respectively, is reported. The hydrogenation reaction operates under mild and eco-benign conditions and can be scaled-up.

Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes.

A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

Cobalt-Catalyzed Cyclization of N-Methoxy Benzamides with Alkynes using an Internal Oxidant through C-H/N-O Bond Activation.

The cyclization of substituted N-methoxy benzamides with alkynes in the presence of an easily affordable cobalt complex and NaOAc provides isoquinolone derivatives in good to excellent yields. The cyclization reaction is compatible with a range of functional group-substituted benzamides, as well as ester- and alcohol-substituted alkynes. The cobalt complex [Co(III) Cp*(OR)2 ] (R=Me or Ac) serves as an efficient catalyst for the cyclization reaction. Later, isoquinolone derivatives were converted into 1-chloro and 1-bromo substituted isoquinoline derivatives in excellent yields in the presence of POCl3 or PBr3 .