Axially Chiral Imidodiphosphoric Acid Catalyst for Asymmetric Sulfoxidation Reaction: Insights on Asymmetric Induction

Jindal, Garima; Sunoj, Raghavan B.

doi:10.1002/ange.201309532

Cited by 20 publications

(3 citation statements)

References 71 publications

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“…57 This level of theory has recently been employed to account for the weak non-covalent interactions. 58 The CNT considered in the DFT study was an armchair single walled carbon nanotube (SWCNT). All the dangling bonds in carbon nanostructures (both CNT and graphene) were linked to the individual hydrogen atoms to compensate the unsatisfied valency of terminal carbon atoms.…”

Section: Dft Methodsmentioning

confidence: 99%

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures

Jana

Tiwari

Vanka

et al. 2016

Phys. Chem. Chem. Phys.

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Emerging nanotechnology has rapidly broadened interfacial prospects of biological molecules with carbon nanomaterials (CNs). A prerequisite for effectively harnessing such hybrid materials is a multi-faceted understanding of their complex interfacial interactions as functions of the physico-chemical characteristics and the surface topography of the individual components. In this article, we address the origins of the curvature dependence of polypeptide adsorption on CN surfaces (CNSs), a phenomenon bearing an acute influence upon the behavior and activity of CN-protein conjugates. Our benchmark molecular dynamics (MD) simulations with the amphiphilic full-length amyloid beta (Aβ) peptide demonstrate that protein adsorption is strongest on the concave (inner) CN surface, weakest on the convex (outer) surface, and intermediary on the planar surface, in agreement with recent experimental reports. The curvature effects, however, are found to manifest non-uniformly between the amino acid subtypes. To understand the underlying interplay of the chemical nature of the amino acids and surface topography of the CNs, we performed high-level quantum chemical (QM) calculations with amino acid analogs (AAA) representing their five prominent classes, and convex, concave and planar CN fragments. Molecular electrostatic potential maps reveal pronounced curvature dependence in the mixing of electron densities, and a resulting variance in the stabilization of the non-covalently bound molecular complexes. Interestingly, our study revealed that the interaction trends of the high-level QM calculations were captured well by the empirical force field. The findings in this study have important bearing upon the design of carbon based bio-nanomaterials, and additionally, provide valuable insights into the accuracy of various computational techniques for probing non-bonded interfacial interactions.

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Section: Dft Methodsmentioning

confidence: 99%

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures

Jana

Tiwari

Vanka

et al. 2016

Phys. Chem. Chem. Phys.

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“…Higher selectivity was obtained by means of imidodiphosphoric acid 26 (Figure 17(a)), which provided oxidation of thioanisole 27 in 98% ee. In order to understand the mode of action of this new class of CBAs, computational studies were undertaken by the group of Sunoj [42]. Calculations showed that the reaction proceeds by coordination of H 2 O 2 by the catalyst and consequent reaction of this complex with the substrate according with the mechanism in Figure 17(b).…”

Section: Stereoselective Sulfoxidationsmentioning

confidence: 99%

Basic principles of substrate activation through non-covalent bond interactions

Orlandi

2020

Physical Sciences Reviews

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AbstractIn the last twenty years, chiral Brønsted acid and chiral counteranion catalysis have emerged as a fundamental area of organocatalysis. The development of chiral acidic catalysts has allowed extending many known Brønsted catalyzed reactions to the stereoselective domain. Moreover, the controlled conditions under which these catalysts can be used, allowed accessing reactivity of increasing complexity with extraordinary selectivity levels. However, compared to the explosion of this branch of organocatalysis in an applicative direction, only little has been done to understand and rationalize the observed reaction outcomes. This is due, in part, to the complex nature of the weak interactions (H-bonds, electrostatic, and dispersion interactions) governing this class of reactions. Here we review relevant mechanistic analyses from both chiral Brønsted acid and chiral counteranion directed catalysis. Both experimental and computational work is included that aimed at unveiling the nature of the interactions governing the a number of reactions. These include the: enantioselective reduction of ketoimines with Hantzsch esters; ring opening reactions of epoxides, oxetanes, aziridinium, and sulfonium ions; stereoselective fluorination of allylic alcohols; oxidative aminations of benzylic thioethers (enantioselective Pummerer reaction). These case studies are analyzed and discussed in order to highlight key features and similarities across the different catalytic systems.

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“…As a result, the availability of them is supported by many synthetic approaches developed by our group and other groups . Based on the work of List and Sunoj, we envisioned that the N–H bond of the substrate sulfenamide 1 can make a great difference, because of the additional hydrogen bonds with bifunctional phosphoric acid (Scheme B). On one hand, the phosphoric acid catalyst could form a hydrogen bond with H 2 O 2 and increase its electrophilic property toward the nucleophilic sulfur .…”

mentioning

confidence: 99%

Chiral Brønsted-Acid-Catalyzed Asymmetric Oxidation of Sulfenamide by Using H₂O₂: A Versatile Access to Sulfinamide and Sulfoxide with High Enantioselectivity

Chen

et al. 2019

ACS Catal.

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Herein, we describe an example of catalytic asymmetric synthesis of sulfinamides. Aromatic sulfenamides were chosen as useful substrates, because of the indispensable N−H bond, which could form an efficient hydrogen bond with chiral phosphoric acid. H 2 O 2 (35%) was used as the terminal oxidant for preparation of sulfinamides in high yields and enantioselectivities, which could be easily derivatized to sulfoxides and other sulfinamides without loss of the enantioselectivity.

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Axially Chiral Imidodiphosphoric Acid Catalyst for Asymmetric Sulfoxidation Reaction: Insights on Asymmetric Induction

Cited by 20 publications

References 71 publications

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures

Basic principles of substrate activation through non-covalent bond interactions

Chiral Brønsted-Acid-Catalyzed Asymmetric Oxidation of Sulfenamide by Using H₂O₂: A Versatile Access to Sulfinamide and Sulfoxide with High Enantioselectivity

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Axially Chiral Imidodiphosphoric Acid Catalyst for Asymmetric Sulfoxidation Reaction: Insights on Asymmetric Induction

Cited by 20 publications

References 71 publications

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures

Unraveling origins of the heterogeneous curvature dependence of polypeptide interactions with carbon nanostructures

Basic principles of substrate activation through non-covalent bond interactions

Chiral Brønsted-Acid-Catalyzed Asymmetric Oxidation of Sulfenamide by Using H2O2: A Versatile Access to Sulfinamide and Sulfoxide with High Enantioselectivity

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Product

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Chiral Brønsted-Acid-Catalyzed Asymmetric Oxidation of Sulfenamide by Using H₂O₂: A Versatile Access to Sulfinamide and Sulfoxide with High Enantioselectivity