@article {42697, title = {Reverse-hydroformylation: a missing reaction explored}, journal = {Organic Chemistry Frontiers}, volume = {2}, year = {2015}, month = {AUG}, pages = {1422-1424}, abstract = {

Recent progress in transition-metal catalysed acceptor- and acceptorless-reverse hydroformylation of aldehydes for the conversion of olefins has been discussed. The aldehyde feedstock serves as a source for production of syngas and valuable alkenes.

}, doi = {10.1039/C5QO00229J}, author = {Nandakumar, Avanashiappan and Sahoo, Manoj Kumar and Balaraman, Ekambaram} } @article { ISI:000363389400005, title = {Transition-metal-catalyzed hydrogen-transfer annulations: access to heterocyclic scaffolds}, journal = {Angewandte Chemie-International Edition}, volume = {54}, number = {38}, year = {2015}, month = {SEP}, pages = {11022-11034}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

The ability of hydrogen-transfer transition-metal catalysts, which enable increasingly rapid access to important structural scaffolds from simple starting materials, has led to a plethora of research efforts on the construction of heterocyclic scaffolds. Transition-metal-catalyzed hydrogen-transfer annulations are environmentally benign and highly atom-economical as they release of water and hydrogen as by-product and utilize renewable feedstock alcohols as starting materials. Recent advances in this field with respect to the annulations of alcohols with various nucleophilic partners, thus leading to the formation of heterocyclic scaffolds, are highlighted herein.

}, issn = {1433-7851}, doi = {10.1002/anie.201503247}, author = {Nandakumar, Avanashiappan and Midya, Siba Prasad and Landge, Vinod Gokulkrishna and Balaraman, Ekambaram} } @article {43811, title = {Iron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis}, journal = {Catalysis Science \& Technology}, volume = {7}, year = {2017}, month = {AUG}, pages = {3177-3195}, type = {Article}, abstract = {Inspired by nature, chemists have designed new catalysts in the pursuit of selective bond activation and chemical transformations. Emergent biological systems often use earth-abundant first-row transition elements as catalytically active sites to facilitate specific and highly selective chemical processes. The design of a new catalytic system based on abundant and inexpensive catalysts, particularly the iron-based catalysts, for fundamentally significant synthetic transformations under environmentally benign conditions is an important paradigm in chemical synthesis. In recent times, iron-based catalytic systems have shown unprecedented reactivity in the acceptorless dehydrogenation reactions of feedstock chemicals, with the liberation of molecular hydrogen as the by-product, and have enabled greener chemical synthetic methods and alternative energy storage systems. Indeed, it has been demonstrated that the proper design of iron catalysts by judiciously choosing ligands, can aid in the development of new sustainable energy storage systems and catalysis. This tutorial review focuses on the recent development of iron-based dehydrogenation reactions of fundamentally important feedstock, as a route to sustainable chemical synthesis and energy storage applications. The emerging area of the iron-based dehydrogenation strategy provides an opportunity to make industrially applicable, cost-effective and environmentally benign catalytic systems.}, doi = {10.1039/c7cy00879a}, author = {Balaraman, Ekambaram and Nandakumar, Avanashiappan and Jaiswal, Garima and Sahoo, Manoj K.} } @article {45471, title = { Ni-catalyzed alpha-alkylation of unactivated amides and esters with alcohols by hydrogen auto-transfer strategy }, journal = {CHEMSUSCHEM}, volume = {11}, year = {2018}, month = {NOV}, pages = {3911-3916}, type = {Article}, abstract = {A transition-metal-catalyzed borrowing hydrogen/hydrogen auto-transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C-N and C-C bonds. In this study, a nickel-catalyzed alpha-alkylation of unactivated amides and ester (tert-butyl acetate) is carried out by using primary alcohols under mild conditions. This C-C bond-forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN-pincer complex (0.1-1 mol \%) and proceeds through hydrogen auto-transfer, thereby releasing water as the sole byproduct. In addition, N-alkylation of cyclic amides under Ni-catalytic conditions is demonstrated.}, doi = {10.1002/cssc.201801443}, author = {Midya, Siba P. and Rana, Jagannath and Pitchaimani, Jayaraman and Nandakumar, Avanashiappan and Madhu, Vedichi and Balaraman, Ekambaram} } @article {44603, title = {Pd(II)-Catalyzed gamma-C(sp(3))-H alkynylation of amides: selective functionalization of R chains of amides (RC)-C-1(O)NHR}, journal = {Chemical Communications}, volume = {54}, year = {2018}, month = {JUL}, pages = {7483-7486}, abstract = {

The gamma C(sp(3))-H bond alkynylation of R chains of amides (RC)-C-1(O)NHR, a fundamental class of synthetic substrates, has not been accomplished to date. Here, the first example of palladium(ii)-catalyzed alkynylation of an unactivated gamma C(sp(3))-H bond of alkyl amides (cyclic, linear, and amino acids) is reported. The kinetic experiment shows that the rate of the reaction depends on the coupling partners and the amides. Late-stage diversification of alkynylated amides was developed by utilizing amine and alkyne functionalities.

}, issn = {1359-7345}, doi = {10.1039/c8cc03445a}, author = {Landge, Vinod G. and Parveen, Ayisha and Nandakumar, Avanashiappan and Balaraman, Ekambaram} }