NDLI: Controlling Helical Chirality in Atrane Structures: Solvent-Dependent Chirality Sense in Hemicryptophane-Oxidovanadium(V) Complexes

Please wait, while we are loading the content...

Year: 2017 Volume: 23

Year: 2016 Volume: 22

Year: 2015 Volume: 21

Year: 2014 Volume: 20

Year: 2013 Volume: 19

Year: 2012 Volume: 18

Year: 2011 Volume: 17

Year: 2010 Volume: 16

Year: 2010 Volume: 16 Issue: 48

Year: 2010 Volume: 16 Issue: 47

Year: 2010 Volume: 16 Issue: 46

Year: 2010 Volume: 16 Issue: 45

Year: 2010 Volume: 16 Issue: 44

Year: 2010 Volume: 16 Issue: 43

Year: 2010 Volume: 16 Issue: 42

Year: 2010 Volume: 16 Issue: 41

Year: 2010 Volume: 16 Issue: 40

Year: 2010 Volume: 16 Issue: 39

Year: 2010 Volume: 16 Issue: 38

Year: 2010 Volume: 16 Issue: 37

Year: 2010 Volume: 16 Issue: 36

Year: 2010 Volume: 16 Issue: 35

Year: 2010 Volume: 16 Issue: 34

Year: 2010 Volume: 16 Issue: 33

Year: 2010 Volume: 16 Issue: 32

Year: 2010 Volume: 16 Issue: 31

Year: 2010 Volume: 16 Issue: 30

Year: 2010 Volume: 16 Issue: 29

Year: 2010 Volume: 16 Issue: 28

Year: 2010 Volume: 16 Issue: 27

Year: 2010 Volume: 16 Issue: 26

Year: 2010 Volume: 16 Issue: 25

Year: 2010 Volume: 16 Issue: 24

Year: 2010 Volume: 16 Issue: 23

Year: 2010 Volume: 16 Issue: 22

Year: 2010 Volume: 16 Issue: 21

Year: 2010 Volume: 16 Issue: 20

Year: 2010 Volume: 16 Issue: 19

Year: 2010 Volume: 16 Issue: 18

Year: 2010 Volume: 16 Issue: 17

Year: 2010 Volume: 16 Issue: 16

Year: 2010 Volume: 16 Issue: 15

Year: 2010 Volume: 16 Issue: 14

Year: 2010 Volume: 16 Issue: 13

Year: 2010 Volume: 16 Issue: 12

Year: 2010 Volume: 16 Issue: 11

Year: 2010 Volume: 16 Issue: 10

Year: 2010 Volume: 16 Issue: 9

Year: 2010 Volume: 16 Issue: 8

Year: 2010 Volume: 16 Issue: 7

Year: 2010 Volume: 16 Issue: 6

Year: 2010 Volume: 16 Issue: 5

Year: 2010 Volume: 16 Issue: 4

Year: 2010 Volume: 16 Issue: 3

Year: 2010 Volume: 16 Issue: 2

Synthesis of Iron Oxide Nanoparticles in Listeria innocua Dps (DNA-Binding Protein from Starved Cells): A Study with the Wild-Type Protein and a Catalytic Centre Mutant

The Effect of Backbone Stereochemistry on the Folding of Acyclic $β^{2, 3}-Aminoxy$ Peptides

Reaction Pathways Determined by Mechanical Milling Process for Dehydrogenation/Hydrogenation of the $LiNH_{2}/MgH_{2}$ System

Preparation and Cellular Uptake of pH-Dependent Fluorescent Single-Wall Carbon Nanotubes

Order Versus Disorder in Chiral Tetrathiafulvalene-Oxazoline Radical-Cation Salts: Structural and Theoretical Investigations and Physical Properties

Mechanistic Insights into the Substrate-Controlled Stereochemistry of Glycals in One-Pot Rhodium-Catalyzed Aziridination and Aziridine Ring Opening

Stereoselective Control by Face-to-Face Versus Edge-to-Face Aromatic Interactions: The Case of $C_{3}-Ti^{IV}$ Amino Trialkolate Sulfoxidation Catalysts

A New Zincate-Mediated Rearrangement Reaction of 2-(1-Hydroxyalkyl)-1-alkylcyclopropanol

Analysis of the Detailed Configuration of Hydrated Lanthanoid(III) Ions in Aqueous Solution and Crystalline Salts by Using K- and $L_{3}-Edge$ XANES Spectroscopy

One-Step Preparation of Multifunctional Chitosan Microspheres by a Simple Sonochemical Method

Design and Synthesis of a Highly Sensitive Off–On Fluorescent Chemosensor for Zinc Ions Utilizing Internal Charge Transfer

Alkane Activation over Acidic Zeolites: The First Step

Reactivity of ortho-Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

Synthesis of Highly Efficient Ag@AgCl Plasmonic Photocatalysts with Various Structures

Hydroxypyridinechromene and Pyridinechalcone: Two Coupled Photochromic Systems

Controlling Helical Chirality in Atrane Structures: Solvent-Dependent Chirality Sense in Hemicryptophane-Oxidovanadium(V) Complexes

Evaporation-Induced Ordered Honeycomb Structures of Gold Nanoparticles at the Air/Water Interface

Tungsten(VI) and Tungsten(V) Fluoride Complexes

A Convenient Domino Access to Substituted Alkyl 1,2-Dihydropyridine-3-carboxylates from Propargyl Enol Ethers and Primary Amines

Byproduct-Catalyzed Four-Component Reactions of Aldehydes with Hexamethyldisilazane, Chloroformates, and Nucleophiles in Acetonitrile Leading to Protected Primary Amines, β-Amino Esters, and β-Amino Ketones

Physical Organic Study of Structure–Activity–Enantioselectivity Relationships in Asymmetric Bifunctional Thiourea Catalysis: Hints for the Design of New Organocatalysts

Synthesis of Glycocinnasperimicin D

A New Class of Modular P,N-Ligand Library for Asymmetric Pd-Catalyzed Allylic Substitution Reactions: A Study of the Key Pd–π-Allyl Intermediates

Gold-catalyzed transannular [4+3] cycloaddition reactions.

Silicon- and Tin-Based Cuprates: Now Catalytic in Copper!

A Cruciform 6,6′-Dipentacenyl: Synthesis, Solid-State Packing and Applications in Thin-Film Transistors

A Circular Dichroism Probe for L-Cysteine Based on the Self-Assembly of Chiral Complex Nanoparticles

Reversible $P_{4}$ Activation with Nickel(I) and an $η^{3}-Coordinated$ Tetraphosphorus Ligand between Two $Ni^{I}$ Centers

Carbene stabilization of diarsenic: from hypervalency to allotropy.

Synthesis of Enantiopure Sulfonimidamides and Elucidation of Their Absolute Configuration by Comparison of Measured and Calculated CD Spectra and X-Ray Crystal Structure Determination

Quinoidal Oligothiophenes: Towards Biradical Ground-State Species

Rhodium/Phosphine/Amine⋅HBr Catalyst System for Highly Selective Cross-Cyclodimerization of Aryl- and Alkylalkynes: Efficient Access to Multisubstituted Naphthalene Derivatives

Asymmetric Organocatalytic N-Alkylation of Indole-2-carbaldehydes with α,β-Unsaturated Aldehydes: One-Pot Synthesis of Chiral Pyrrolo[1,2-a]indole-2-carbaldehydes

Synthesis of (Z)-Trisubstituted Olefins by Decarboxylative Grob-Type Fragmentations: Epothilone D, Discodermolide, and Peloruside A

Highly Substituted Furo[3,4-c]azepines by Gold(I)-Catalyzed Diastereoselective Tandem Double Heterocyclizations and 1,2-Alkyl Migration

Substantial Inverse Isotope Effects in the Hydrogen Atom Abstraction from $[(L)ClRh^{III}H/D]^{+}$ Macrocyclic Complexes by Methyl Radicals in Aqueous Solutions

Ring-Closing Metathesis and Photo-Fries Reaction for the Construction of the Ansamycin Antibiotic Kendomycin: Development of a Protecting Group Free Oxidative Endgame

The Effect of Heavy Atoms on Photoinduced Electron Injection from Nonthermalized and Thermalized Donor States of $M^{II}–Polypyridyl$ (M=Ru/Os) Complexes to Nanoparticulate $TiO_{2}$ Surfaces: An Ultrafast Time-Resolved Absorption Study

A Chiral Pyrrolic Tripodal Receptor Enantioselectively Recognizes β-Mannose and β-Mannosides

Cyclometallation and Hydrogen/Deuterium Exchange Reactions of an Arylphosphine Ligand upon Coordination to $\{Ir(η^{5}-C_{5}Me_{5})\}$

Year: 2010 Volume: 16 Issue: 1

Year: 2009 Volume: 15

Year: 2008 Volume: 14

Year: 2007 Volume: 13

Year: 2006 Volume: 12

Year: 2005 Volume: 11

Year: 1997 Volume: 3

Controlling Helical Chirality in Atrane Structures: Solvent-Dependent Chirality Sense in Hemicryptophane-Oxidovanadium(V) Complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Martinez, Alexandre Dutasta, Jean-pierre Gornitzka, Heinz Robert, Vincent
Description	Author Affiliation: Martinez A ( Laboratoire de Chimie, CNRS, Ecole Normale Supérieure de Lyon, 46 Allée d'Italie, 69364 Lyon 07, France.)
Abstract	The diastereomeric hemicryptophane oxidovanadium(V) complexes (P)-(S,S,S)-3 and (M)-(S,S,S)-4 have been synthesized. $^{1}H$ and $^{51}V NMR$ spectra in solution are consistent with the formation of Λ and Δ forms of the propeller-like vanatrane moiety, leading to two diastereomeric conformers for each complex: that is, (P)-(S,S,S-Λ)-3/(P)-(S,S,S-Δ)-3 and (M)-(S,S,S-Λ)-4/(M)-(S,S,S-Δ)-4. The Λ/Δ ratio is rather temperature-insensitive but strongly dependent on the solvent (the de of (M)-(S,S,S)-4 changes from 0 in benzene to 92 % in DMSO). The solvent therefore controls the preferential clockwise or anticlockwise orientation of the propeller-like atrane unit. The energy barriers for the Λ⇄Δ equilibrium were determined by NMR experiments, and the highest $ΔG^{≠}$ value $(103.7 kJ mol^{−1})$ was obtained for (P)-(S,S,S)-3, much higher than those reported for other atrane derivatives. This is attributed to the constraints arising from the cage structure. Determination of the activation parameters provides evidence for a concerted, rather than a stepwise, interconversion mechanism with entropies $(ΔS^{≠})$ of −243 and $−272 J mol^{−1} K^{−1}$ for (P)-(S,S,S)-3 and (M)-(S,S,S)-4, respectively. The molecular structure of the (P)-(S,S,S-Λ)-3 isomer was solved by X-ray diffraction and shows a distorted structure with one of the linkers located in the CTV cavity. Complementary quantum chemical calculations were carried out to obtain the energy-minimized structures of (P)-(S,S,S)-3 and (M)-(S,S,S)-4. Our density functional theory calculations suggest that the (P)-(S,S,S-Λ)-3 is favored, in agreement with experimental data. For the M series, a similar strategy was used to extract molecular structures and relative energies. As in the case of the P diastereomer, the Λ form dominates over the Δ one.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	2
Volume Number	16
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2010-01-11
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Organometallic Compounds Chemical Synthesis Triazoles Vanadium Chemistry Models, Molecular Molecular Structure Polycyclic Compounds Stereoisomerism Thermodynamics
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

Central Library (ISO-9001:2015 Certified)
Indian Institute of Technology Kharagpur
Kharagpur, West Bengal, India | PIN - 721302

See location in the Map
03222 282435
Mail: support@ndl.gov.in

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in