List Of Publications
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Publication 7
Publication 6
Parnitzke, B.; Gerhardt, E.§; Lalisse R.§; Maity, T.§; Xuan, Z.; Gutierrez, O.* Derosa, J.* A Voltage-Controlled Redox Mediator Strategy Enables Electrocatalytic Z-Selective Semi-Hydrogenation. ACS Catal. Just accepted
Publication 5
Lewis acids play a central role in a large variety of chemical transformations. The reactivity of the strongest Lewis acids is typically studied in the context of affinity towards hard bases, such as fluoride or oxygenous species. Carbocations can be viewed as soft Lewis acids, possessing significant affinity for softer bases, such as hydride. This work presents the ambient-temperature isolation of salts of the perfluorotrityl cation ((C6F5)3C+or F15Tr+) in combination with halogenated carborane anions. The F15Tr+ cation exhibits remarkable hydride affinity, illustrated by the observation of hydride abstraction from dihydrogen, and of the rapid abstraction of hydride from −CH2−groups in alkanes. Theoretical studies support the favorability of hydride abstraction from dihydrogen, and indicate that the hydride abstraction from alkanes proceeds via a concerted hydride transfer process that is sensitive to steric effects.
Publication 4
An elegant synthesis of pyrrole-2-carboxylic acid anhydrides from pyrrole-2-carboxaldehydes using TBAI as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant is described herein. Unlike the previous reports wherein pyrrole-2-carboxylic acids were invariably used, we report here for first time the oxidative self-coupling of N-benzyl pyrrole-2-carboxaldehydes for the synthesis of 1-benzyl-1H-pyrrole-2-carboxylic anhydrides. In addition, a one-pot synthesis of novel pyrrole-2-carboxamides from pyrrole-2-carboxaldehydes is also reported. The mechanistic investigation supports a previously unexplored oxidative self-coupling of a pyrrole acyl radical, leading to the synthesis of a carboxylic anhydride.
Publication 3
Modular, catalytic, and stereoselective methods for the dicarbofunctionalization of alkenes can streamline the synthesis of chiral active pharmaceutical ingredients (APIs) and agrochemicals. However, despite the inherent attractive properties of iron as catalysts for practical pharmaceutical synthesis (i.e., less expensive, more abundant, less toxic, and lower carbon footprint in comparison to other transition metals), iron-based catalytic methods that enable highly stereoselective dicarbofunctionalization of alkenes are lacking. Herein, we report the use of readily available chiral vinyl oxazolidinones as effective chiral radical lynchpins to enable practical and diastereoselective (up to 1:78 dr) Fe-catalyzed dicarbofunctionalization with fluoroalkyl halides and hetero(aryl) Grignard reagents. Experimental and computational mechanistic studies are carried out to elucidate the origin of stereoinduction and to build a stereochemical model for the rational reaction design.
Publication 2
A new method for formylation of nitrogen heterocycles overcoming the limitations of classical approaches using a cheap feedstock formylating agent especially under mild and neutral conditions is the subject of this current investigation. This work describes direct formylation of nitrogen heterocycles (azaindoles, indoles, pyrroles) and anilines using glyoxylic acid as the formyl source and K2S2O8 as the exclusive reagent. The key features include a general method for both C- and N-formylation under neutral and mild reaction conditions. The application of the method is further demonstrated in the tandem synthesis of nitrogen heterocycles, pharmaceuticals, and a natural product. Unlike aroylation with arylglyoxylic acids, a previously unknown pathway for the direct formylation with glyoxylic acid in the presence of K2S2O8 is now unveiled.
Publication 1
