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  1. Asymmetric synthesis of substituted 1,4 cyclohexadienes and cyclobutenes has received great attention in recent years. Strategies such as base metal catalyzed cycloaddition bypass the need of harsh reaction conditions which are often required for synthesis of such motifs. These strategies using base-metals as catalysts are also valuable in constructing substituted cyclic motifs from readily available and inexpensive materials such as dienes and alkynes. Such reactions can be cost effective and environmentally friendly. In past decade, low valent cobalt has shown promising reactivity in forming new C-C and C-X (e. g., X= Si, B, N) bonds in high stereoselectivity. Through our studies, we found that cationic cobalt(I) complexes can catalyze intermolecular cycloaddition reactions of alkyne and 1,3-dienes in regio-and enantioselective manner. We also discovered that the involvement of 4 pi electrons or 2 pi electrons of 1,3-dienes can be controlled by the judicious choice of ligands employed on cobalt leading to [4+2] and [2+2] cycloaddition products respectively in high regio- and stereoselectivity. This excellent selectivity complimented with moderate to good yields provided us with broadly applicable protocol for synthesis of diversely substituted enantiopure cyclic motifs with enantiomeric excesses upto 99%. The scope of this method has been expanded over simple aliphatic and aromatic 1,3-dienes and alkynes bearing various functional groups. The methodical development of this transformation along with the ligand effects and possible mechanisms will be discussed in detail. 
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  2. Asymmetric synthesis of substituted 1,4 cyclohexadienes and cyclobutenes has received great attention in recent years. Strategies such as base metal catalyzed cycloaddition bypass the need of harsh reaction conditions which are often required for synthesis of such motifs. These strategies using base-metals as catalysts are also valuable in constructing substituted cyclic motifs from readily available and inexpensive materials such as dienes and alkynes. Such reactions can be cost effective and environmentally friendly. In past decade, low valent cobalt has shown promising reactivity in forming new C-C and C-X (e. g., X= Si, B, N) bonds in high stereoselectivity. Through our studies, we found that cationic cobalt(I) complexes can catalyze intermolecular cycloaddition reactions of alkyne and 1,3-dienes in regio-and enantioselective manner. We also discovered that the involvement of 4-pi electrons or 2-pi electrons of 1,3-dienes can be controlled by the judicious choice of ligands employed on cobalt leading to [4+2] and [2+2] cycloaddition products respectively in high regio- and stereoselectivity. This excellent selectivity complimented with moderate to good yields provided us with broadly applicable protocol for synthesis of diversely substituted enantiopure cyclic motifs with enantiomeric excesses upto 99%. The scope of this method has been expanded over simple aliphatic and aromatic 1,3-dienes and alkynes bearing various functional groups. The methodical development of this transformation along with the ligand effects and possible mechanisms will be discussed in detail. 
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  3. From 1875 to 1878, concurrent multiyear droughts in Asia, Brazil, and Africa, referred to as the Great Drought, caused widespread crop failures, catalyzing the so-called Global Famine, which had fatalities exceeding 50 million people and long-lasting societal consequences. Observations, paleoclimate reconstructions, and climatemodel simulations are used 1) to demonstrate the severity and characterize the evolution of drought across different regions, and 2) to investigate the underlying mechanisms driving its multiyear persistence. Severe or record-setting droughts occurred on continents in both hemispheres and in multiple seasons, with the ‘‘Monsoon Asia’’ region being the hardest hit, experiencing the single most intense and the second most expansive drought in the last 800 years. The extreme severity, duration, and extent of this global event is associated with an extraordinary combination of preceding cool tropical Pacific conditions (1870–76), a record-breaking El Niño (1877–78), a record strong Indian Ocean dipole (1877), and record warm North Atlantic Ocean (1878) conditions. Composites of historical analogs and two sets of ensemble simulations—one forced with global sea surface temperatures (SSTs) and another forced with tropical Pacific SSTs—were used to distinguish the role of the extreme conditions in different ocean basins. While the drought in most regions was largely driven by the tropical Pacific SST conditions, an extreme positive phase of the Indian Ocean dipole and warm NorthAtlantic SSTs, both likely aided by the strong El Niño in 1877–78, intensified and prolonged droughts in Australia and Brazil, respectively, and extended the impact to northern and southeastern Africa. Climatic conditions that caused the Great Drought and Global Famine arose from natural variability, and their recurrence, with hydrological impacts intensified by global warming, could again potentially undermine global food security. 
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  5. Free, publicly-accessible full text available December 1, 2024