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    Enantionmeros Solomon 10th Edition

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    Leonardo Arriagada
    This document discusses different types of chirality and stereoisomers. It begins by explaining that any tetrahedral atom with four different groups attached is a chirality center, and provides examples of compounds containing chirality centers of silicon, germanium, nitrogen, and sulfur. It then notes that some molecules can be chiral even without a chirality center if they have restricted bond rotation that results in stable, isolatable conformational isomers called atropisomers. An example of this is BINAP, which is chiral due to restricted rotation between its naphthalene rings. The document concludes by explaining that allenes can also exhibit stereoisomerism due to the perpendicular planes of their double bonds, resulting in

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    Enantionmeros Solomon 10th Edition

    Uploaded by

    Leonardo Arriagada
    6 views2 pages
    This document discusses different types of chirality and stereoisomers. It begins by explaining that any tetrahedral atom with four different groups attached is a chirality center, and provides examples of compounds containing chirality centers of silicon, germanium, nitrogen, and sulfur. It then notes that some molecules can be chiral even without a chirality center if they have restricted bond rotation that results in stable, isolatable conformational isomers called atropisomers. An example of this is BINAP, which is chiral due to restricted rotation between its naphthalene rings. The document concludes by explaining that allenes can also exhibit stereoisomerism due to the perpendicular planes of their double bonds, resulting in

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    This document discusses different types of chirality and stereoisomers. It begins by explaining that any tetrahedral atom with four different groups attached is a chirality center, and provides examples of compounds containing chirality centers of silicon, germanium, nitrogen, and sulfur. It then notes that some molecules can be chiral even without a chirality center if they have restricted bond rotation that results in stable, isolatable conformational isomers called atropisomers. An example of this is BINAP, which is chiral due to restricted rotation between its naphthalene rings. The document concludes by explaining that allenes can also exhibit stereoisomerism due to the perpendicular planes of their double bonds, resulting in

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    6 views2 pages

    Enantionmeros Solomon 10th Edition

    Uploaded by

    Leonardo Arriagada
    This document discusses different types of chirality and stereoisomers. It begins by explaining that any tetrahedral atom with four different groups attached is a chirality center, and provides examples of compounds containing chirality centers of silicon, germanium, nitrogen, and sulfur. It then notes that some molecules can be chiral even without a chirality center if they have restricted bond rotation that results in stable, isolatable conformational isomers called atropisomers. An example of this is BINAP, which is chiral due to restricted rotation between its naphthalene rings. The document concludes by explaining that allenes can also exhibit stereoisomerism due to the perpendicular planes of their double bonds, resulting in

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    solom_c05_186-229hr.

    qxd 28-09-2009 14:28 Page 224

    224 Chapter 5 Stereochemistry

    5.17 Compounds with Chirality Centers Other than Carbon


    Any tetrahedral atom with four different groups attached to it is a chirality center. Shown
    here are general formulas of compounds whose molecules contain chirality centers other
    than carbon. Silicon and germanium are in the same group of the periodic table as carbon.
    They form tetrahedral compounds as carbon does. When four different groups are situated
    around the central atom in silicon, germanium, and nitrogen compounds, the molecules are
    chiral and the enantiomers can, in principle, be separated. Sulfoxides, like certain exam-
    ples of other functional groups where one of the four groups is a nonbonding electron pair,
    are also chiral. This is not the case for amines, however (Section 20.2B):
    R4 R3 H R3 R4 R3 R2 R1
    Si Ge N+ X– S
    R1 R2 R1 R2 R1 R2 O

    5.18 Chiral Molecules That Do Not Possess a Chirality Center


    A molecule is chiral if it is not superposable on its mirror image. The presence of a tetrahe-
    dral atom with four different groups is only one type of chirality center, however. While most
    of the chiral molecules we shall encounter have chirality centers, there are other structural attrib-
    utes that can confer chirality on a molecule. For example, there are compounds that have such
    large rotational barriers between conformers that individual conformational isomers can be sep-
    arated and purified, and some of these conformational isomers are stereoisomers.
    Conformational isomers that are stable, isolable compounds are called atropisomers. The
    existence of chiral atropisomers has been exploited to great effect in the development of chiral
    catalysts for stereoselective reactions. An example is BINAP, shown below in its enantiomeric
    forms:

    P(Ph)2 (Ph)2P
    P(Ph)2 (Ph)2P

    (S)-BINAP (R)-BINAP

    The origin of chirality in BINAP is the restricted rotation about the bond between the two
    nearly perpendicular naphthalene rings. This torsional barrier leads to two resolvable enan-
    tiomeric conformers, (S)- and (R)-BINAP. When each enantiomer is used as a ligand for
    metals such as ruthenium and rhodium (bound by unshared electron pairs on the phosphorus
    atoms), chiral organometallic complexes result that are capable of catalyzing stereoselec-
    tive hydrogenation and other important industrial reactions. The significance of chiral lig-
    ands is highlighted by the industrial synthesis each year of approximately 3500 tons of
    (⫺)-menthol using an isomerization reaction involving a rhodium (S)-BINAP catalyst.
    Allenes are compounds that also exhibit stereoisomerism. Allenes are molecules that
    contain the following double-bond sequence:

    C C C

    The planes of the ␲ bonds of allenes are perpendicular to each other:


    R´
    R´
    C C C
    R
    R
    solom_c05_186-229hr.qxd 28-09-2009 14:28 Page 225

    Problems 225

    H H
    H H
    C" C" C C"C" C Figure 5.22 Enantiomeric forms of 1,3-dichloroallene. These two
    Cl Cl
    Cl Cl molecules are nonsuperposable mirror images of each other and
    are therefore chiral. They do not possess a tetrahedral atom with
    Mirror four different groups, however.

    This geometry of the p bonds causes the groups attached to the end carbon atoms to lie in
    perpendicular planes, and, because of this, allenes with different substituents on the end
    carbon atoms are chiral (Fig. 5.22). (Allenes do not show cis–trans isomerism.)

    In This Chapter
    In this chapter you learned that the handedness of life begins at the molecular level.
    Molecular recognition, signaling, and chemical reactions in living systems often hinge on
    the handedness of chiral molecules. Molecules that bear four different groups at a tetrahe-
    dral carbon atom are chiral if they are nonsuperposable with their mirror image. The atoms
    bearing four different groups are called chirality centers.
    Mirror planes of symmetry have been very important to our discussion. If we want to
    draw the enantiomer of a molecule, one way to do so is to draw the molecule as if it were
    reflected in a mirror. If a mirror plane of symmetry exists within a molecule, then it is achi-
    ral (not chiral), even if it contains chirality centers. Using mirror planes to test for sym-
    metry is an important technique.
    In this chapter you learned how to give unique names to chiral molecules using the
    Cahn–Ingold–Prelog R,S–system. You have also exercised your mind’s eye in visualizing mol-
    ecular structures in three dimensions, and you have refined your skill at drawing three-dimen-
    sional molecular formulas. You learned that pairs of enantiomers have identical physical
    properties except for the equal and opposite rotation of plane-polarized light, whereas diastere-
    omers have different physical properties from one another. Interactions between each enan-
    tiomer of a chiral molecule and any other chiral material lead to diastereomeric interactions,
    which lead to different physical properties that can allow the separation of enantiomers.
    Chemistry happens in three dimensions. Now, with the information from this chapter
    building on fundamentals you have learned about molecular shape and polarity in earlier
    chapters, you are ready to embark on your study of the reactions of organic molecules.
    Practice drawing molecules that show three dimensions at chirality centers, practice nam-
    ing molecules, and label their regions of partial positive and negative charge. Paying atten-
    tion to these things will help you learn about the reactivity of molecules in succeeding
    chapters. Most important of all, do your homework!

    Key Terms and Concepts


    The key terms and concepts that are highlighted in bold, blue text within the chapter are
    defined in the glossary (at the back of the book) and have hyperlinked definitions in the
    accompanying WileyPLUS course (www.wileyplus.com).

    Problems
    Note to Instructors: Many of the homework problems are available for assignment via WileyPLUS, an online
    teaching and learning solution.

    CHIRALITY AND STEREOISOMERISM


    5.33 Which of the following are chiral and, therefore, capable of existing as enantiomers?
    (a) 1,3-Dichlorobutane (d) 3-Ethylpentane (g) 2-Chlorobicyclo[2.1.1]hexane
    (b) 1,2-Dibromopropane (e) 2-Bromobicyclo[1.1.0]butane (h) 5-Chlorobicyclo[2.1.1]hexane
    (c) 1,5-Dichloropentane (f) 2-Fluorobicyclo[2.2.2]octane

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