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Related Concept Videos

Stereoisomerism of Cyclic Compounds02:33

Stereoisomerism of Cyclic Compounds

In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
Naming Enantiomers02:21

Naming Enantiomers

The naming of enantiomers employs the Cahn–Ingold–Prelog rules that involve assigning priorities to different substituent groups at a chiral center. Each enantiomer, being a distinct molecule, is assigned a unique name by the Cahn–Ingold–Prelog (CIP) rules, also called the R–S system. The prefix R- or S- attached to the chiral centers in an enantiomer is dependent on the spatial arrangement of the four substituents on the chiral center. The R–S system essentially comprises three steps:...
Radical Halogenation: Stereochemistry01:33

Radical Halogenation: Stereochemistry

Stereochemistry is the study of the different spatial arrangements of atoms in a given molecule. The stereochemistry of radical halogenations can be understood from three different situations:
Halogenation to form a new chiral center:
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
SN2 Reaction: Stereochemistry02:23

SN2 Reaction: Stereochemistry

In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
SN1 Reaction: Stereochemistry02:15

SN1 Reaction: Stereochemistry

This lesson provides an in-depth discussion of the stereochemical outcomes in an SN1 reaction.
In the first step of an SN1 reaction, the bond between the electrophilic carbon and the leaving group ionizes to generate the carbocation intermediate. The second step of the mechanism is the nucleophilic attack.
In the formed carbocation, the positively charged carbon is sp2 hybridized with a trigonal planar geometry. As all the three substituents lie on the same plane, a plane of symmetry for the...

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Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy
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Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy

Published on: September 17, 2017

An introduction to stereochemical restraints.

Philip R Evans1

  • 1MRC Laboratory of Molecular Biology, Hills Road, Cambridge CB2 2QH, England. pre@mrc-lmb.cam.ac.uk

Acta Crystallographica. Section D, Biological Crystallography
|December 14, 2006
PubMed
Summary

Stereochemical restraints are crucial for determining accurate macromolecular structures from X-ray crystallography data. These restraints ensure chemical reasonableness by defining bond lengths, angles, and other molecular properties.

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Area of Science:

  • Structural biology
  • Crystallography
  • Biochemistry

Background:

  • X-ray crystallography data at typical resolutions are insufficient for ab initio structure determination.
  • Stereochemical information is essential to derive chemically plausible molecular models.

Purpose of the Study:

  • To describe the definition and origin of stereochemical restraints used in macromolecular structure refinement.
  • To explain the role of restraints in ensuring the accuracy of crystallographic models.

Main Methods:

  • Utilizing stereochemical restraints including bond lengths, bond angles, planarity, and chiral volumes.
  • Employing a dictionary containing atom types, connectivity, and restraint values.
  • Defining ring puckering in flexible sugars using torsion angles.

Main Results:

  • Stereochemical restraints are indispensable for obtaining chemically sound macromolecular structures.
  • A comprehensive dictionary facilitates the application of appropriate restraints.
  • Torsion angles, while not typically restrained, possess optimal values influencing substituent positions.

Conclusions:

  • The integration of stereochemical restraints is fundamental to accurate X-ray crystallographic structure determination.
  • Proper definition and application of restraints, including those for flexible rings, enhance structural model reliability.