Chart of Definitions and Interrelationships of the Different Kinds of Isomers

Isomers may be:

Skeletal (structural) isomers, which have different atom-to-atom connections. Stereoisomers, which have the same atom-to-atom connections, but nonsuperimposable shapes. Stereoisomers may be: o Diastereomers, which have different internal dimensions (distances between nonbonded atoms, dihedral angles, etc.), and are not mirror images; or, o Enantiomers, which have identical internal dimensions, and are nonsuperimposable mirror images. Stereoisomers may also be:
o o

Configurational stereoisomers, which can be interconverted only by breaking or bonds, or by changing the configurations of stereocenters; or, Conformational stereoisomers, which can be interconverted by rotation about bonds (including chair flips) or by lone pair inversion. interconversion requires changing the configurations of stereocenters configurational diastereomers (cis/trans, E/Z) configurational enantiomers can be interconverted by rotation about bonds or by lone pair inversion conformational diastereomers (staggered/eclipsed, anti/gauche, axial/equatorial) conformational enantiomers

Stereoisomers
different internal dimensions nonsuperimposable mirror images

Note: The terms 'diastereomer' and 'enantiomer' refer to 'configurational diastereomer' and 'configurational enantiomer' unless otherwise specified.

FLOW CHART FOR DETERMINING THE RELATIONSHIP BETWEEN TWO STRUCTURES

Determining stereochemical relationships between two structures:
Two structures that have the same atom-to-atom connections may be configurational diastereomers, configurational enantiomers, or homomers. (Two homomers may differ in their conformation, of course.) Two compounds that have the same configuration at all of their stereocenters are homomers. Two compounds that differ at some but not all of their sp3 stereocenters or at any of their sp2 stereocenters are configurational diastereomers.

Two compounds that differ at all of their sp3 stereocenters and at none of their sp2 stereocenters are configurational enantiomers (if they are chiral) or homomers (if they are achiral). NOTE: Allenes and iminoketenes, R2C=C=CR2 and R2C=C=NR, in which the two R groups on each of the terminal C atoms are different, are treated as a single sp3 stereocenter.

Determining the chirality of a compound:

A compound that has no sp3 stereocenters must be achiral overall. However, it may have chiral conformers, and those chiral conformers may be lowest in energy, and sometimes there may even be a large steric barrier to interconversion of the conformational enantiomers. A compound that has one sp3 stereocenter must be chiral. A compound that has more than one sp3 stereocenter may or may not be chiral. If it has a plane of symmetry, it is achiral. If it lacks a plane of symmetry, it is probably chiral. NOTE: Allenes and iminoketenes, R2C=C=CR2 and R2C=C=NR, in which the two R groups on each of the terminal C atoms are different, are treated as a single sp3 stereocenter.

GLOSSARY OF STEREOCHEMICAL TERMS

The following glossary may help you learn the terminology and jargon of stereochemistry and to what situations the different terms apply.

A means that the term refers to an atom or a group of atoms within a molecule. M means that the term refers to a single molecule or structure. R means that the term refers to a molecule's or structure's relationship to another molecule or structure. S means that the term refers to a macroscopic sample of a compound, i.e. a large collection of molecules. X means that the term refers to a reaction.

At the end of this glossary the terms are listed according to this scheme. Terms in (parentheses) represent sloppy usage commonly found in the literature. You may want to visit the IUPAC nomenclature Web site for more information. (A) (1) Originally, trans to the axial substituent at C(10) in diterpenoids and steroids. (2) Now, most commonly refers to an atom or group that is pointing down or away from the reader as the structure is drawn. (3) In cyclic sugars, a diastereomer in which the anomeric OR group is trans to the CH2OR group. (The convention is to draw D-sugars with the CH2OH group pointing up, so an -OH group will be trans to the CH2OH group. However, the trans definition for -sugars is retained for L-sugars, even though their CH2OH group may point down.) Contrast to . Examples. Achiral (M) Identical to one's mirror image. An achiral structure has a plane of symmetry (usually), a center of inversion, or an improper axis of symmetry. An achiral structure does not have an enantiomer. Achiral compound (M) A compound that has at least one energetically accessible achiral ground state or transition state conformation. (Note that this property is dependent on the time scale. A conformation that is not energetically accessible on the time scale of nanoseconds may be accessible on the time scale of minutes.) An achiral compound does not have a configurational enantiomer. Contrast to chiral compound. Anomer (R) An epimer at a C atom in the ketone/aldehyde oxidation state. Mostly used to refer to cyclic sugars. Anti (A,X) (1) Describes the relative stereochemistry of two substituents on an acyclic chain in a molecule. If the chain is drawn in horizontal, zigzag fashion and one substituent is pointing out and the other in, they are anti. Examples. (2) The relationship of two substituents, A and D, on two adjacent atoms, B and C, when the A-B-C-D dihedral angle is 180. (3) Describes a reaction in which two groups add to opposite faces of a bond. Contrast to syn. Asymmetric center (A) Same as stereogenic atom.

Asymmetric compound (M) A compound with no improper or proper axis of symmetry except the C1 axis. Atropisomer (R) A conformational stereoisomer of a reference compound that converts to the reference compound only slowly on the NMR or laboratory time scale. Axial chirality (M) Describes the shape of certain chiral molecules that lack a tetrahedral stereocenter. The substituents on these molecules can be regarded as residing at the four corners of a stretched tetrahedron. The axis along which the tetrahedron has been stretched is the axis of chirality. Examples. Contrast to (planar chirality). Axis of symmetry (M) An imaginary line through a compound. Rotation of the compound by an integral fraction of a circle around this axis (1/2, 1/3, etc.) brings the compound to superposition on itself. An axis of symmetry is represented by Cn, where n is the integral fraction. Also called proper axis of symmetry. Contrast to improper axis of symmetry and plane of symmetry. (A) (1) Originally, cis to the axial substituent at C(10) in diterpenoids and steroids. (2) Now, most commonly refers to an atom or group that is pointing up or towards the reader as the structure is drawn. (3) In cyclic sugars, a diastereomer in which the anomeric OR group is cis to the CH2OR group. (The convention is to draw D-sugars with the CH2OH group pointing up, so a -OH group will be cis to the CH2OH group. However, the cis definition for -sugars is retained for L-sugars, even though their CH2OH group may point down.) Contrast to . Examples. Cn axis (n is an integer) (M) Same as axis of symmetry. Center of inversion (M) An imaginary point in a compound. Reflection of the compound through this point brings the compound to superposition on itself. An inversion center is represented by i. Same as an S2 improper axis of symmetry. Chiral (M) Not identical to one's mirror image. A chiral structure lacks a plane of symmetry, a center of inversion, and an improper axis of symmetry. A chiral structure has an enantiomer. Contrast to achiral. Chiral center (A) A tetrahedral stereogenic atom. Chiral compound (M) A compound that does not have an energetically accessible achiral ground state or transition state conformation. (Note that this property is dependent on the time scale. A conformation that is not energetically accessible on the time scale of nanoseconds may be accessible on the time scale of minutes.) A chiral compound has a configurational enantiomer. Contrast to achiral compound. Cis (A,M) (1) Describes the stereochemical relationship of two groups on different C atoms of an alkene. If the XC=CY dihedral angle is 0, the groups are cis. (2) Describes a 1,2-disubstituted alkene whose substituents are cis. (3) Describes the stereochemical relationship of two groups on different tetrahedral C atoms of a single ring in a cyclic compound. Considering the atoms of the ring to be coplanar, if the two groups reside on the same face of the plane, the groups are cis. (4) Describes a 1,n-disubstituted cyclic compound with two substituents that are cis to one another. Contrast to trans.

Configuration (A) The spatial arrangement of groups around a stereogenic atom (R or S) or an alkene (E or Z). Configurational diastereomer (R) A diastereomer of a reference compound that can be converted to it only by breaking covalent bonds, for example by inverting the configurations of some but not all of the stereocenters in a compound. Configurational enantiomer (R) An enantiomer of a reference compound that can be converted to it only by breaking covalent bonds, for example by inverting the configurations of all of the tetrahedral stereocenters in a compound. Configurational purity (S) The extent to which the molecules in a sample of a compound have a particular stereocenter in the same configuration. Configurational stereoisomer (R) A stereoisomer of a reference compound that can be converted to it only by breaking covalent bonds, for example by inverting the configurations of some or all of the stereocenters in a compound. Refers to either configurational enantiomers or configurational diastereomers. Configurationally pure (S) Describes a sample in which all the molecules in the sample have a particular stereocenter in the same configuration. Conformation (M) The spatial arrangement of atoms in a molecule that can be adjusted or changed by rotations about sigma bonds or by lone pair inversions. Conformational diastereomer (R) A diastereomer of a reference structure that can be converted to it by rotations about sigma bonds or by lone pair inversions. Conformational enantiomer (R) An enantiomer of a reference structure that can be converted to it by rotations about sigma bonds or by lone pair inversions. Conformational stereoisomer (R) A stereoisomer of a reference structure that can be converted to it by rotations about sigma bonds or by lone pair inversions. Refers to either conformational enantiomers or conformational diastereomers. Conformer (R) Same as conformational stereoisomer. Constitutional isomer (R) Same as structural isomer. (M) An archaic term designating the absolute stereochemistry of carbohydrates (sugars) and amino acids. A molecule is D when the arrangement of groups around a stereocenter is the same as the arrangement of groups about the stereocenter of (R)-glyceraldehyde (2,3dihydroxypropanal). In carbohydrates with multiple stereocenters, the stereocenter furthest from the C in the aldehyde or carboxylic acid oxidation state determines the absolute stereochemistry. Naturally occurring carbohydrates are mostly D. Not to be confused with dextrorotatory! Contrast to L.
D

Dextrorotatory (M,S) Rotates the plane of plane-polarized light clockwise, in the (+) direction. Contrast to levorotatory.

Diastereomer (R) (1) A stereoisomer of a reference compound or structure that has a shape that is not the mirror image of the reference compound or structure. Diastereomers have different internal dimensions (interatomic distances, dihedral angles) and different energies. (2) In common usage, same as configurational diastereomer. Diastereoselective (X) A reaction in which more of one diastereomer is obtained than another. Diastereospecific (X) A reaction in which the mechanism requires that only one diastereomer be obtained. Diastereotopic (A) Refers to the relationship between two atoms of the same element or two groups of the same composition in a compound. Diastereotopic atoms or groups have the same atom-to-atom connections, and their environments do not exchange by free rotation about bonds or lone pair inversion, and they cannot be related by an axis of symmetry. Diastereotopic atoms or groups have different reactivities and spectroscopic properties. Examples: The two H atoms on C(3) of 2-butanol; the two H atoms on C(1) on propene. Contrast to enantiotopic and homotopic. Dissymmetric compound (M) Same as chiral. E (M) Designates the configuration of an alkene. The four substituents of the alkene are assigned priorities. The alkene has the E configuration when the higher priority substituent on one C is trans to the higher priority substituent on the other C. Contrast to Z. Examples. ee (S) Same as enantiomeric excess. Enantioenriched (S) Same as enantiomerically enriched. Enantiomer (R) (1) A stereoisomer of a reference compound or structure that is the nonsuperimposable mirror image of the reference compound or structure. Enantiomers have identical internal dimensions (interatomic distances, dihedral angles) and identical energies, but they rotate plane-polarized light in equal but opposite directions, and they interact with other chiral objects in different ways. Structures that have enantiomers are always chiral. (2) In common usage, same as configurational enantiomer. Enantiomeric excess (ee) (S) The excess of one enantiomer over racemic material in a sample of a chiral compound. Defined as (er 1) / (er + 1), and expressed as a percentage. A racemic sample has an ee of 0%; an enantiomerically pure sample has an ee of 100%. The ee of a sample of a compound can be measured by dividing the specific rotation of the sample by the specific rotation of an enantiomerically pure sample of the same compound. Enantiomeric ratio (er) (S) The ratio of the amounts of the two enantiomers in a particular sample of a chiral compound. Enantiomerically enriched (S) A sample of a chiral compound that consists of more of one enantiomer than the other. The extent to which a sample is enantiomerically enriched is quantified by the enantiomeric ratio or the enantiomeric excess.

Enantiomerically pure (S) A sample of a chiral compound that consists of a single enantiomer. Enantiopure (S) Same as enantiomerically pure. Enantioselective (X) A reaction in which more of one enantiomer is obtained than the other. Enantiotopic (A) Refers to the relationship between two atoms of the same element or two groups of the same composition in a compound. Enantiotopic atoms or groups have the same atom-to-atom connections, and their environments do not exchange by free rotation about bonds or lone pair inversion, but they can be related by an improper axis of symmetry in at least one conformation. Enantiotopic atoms or groups have identical reactivities and spectroscopic properties unless they are placed in a chiral environment (such as a chiral solvent). Example: The two H atoms on C(3) of 2-butanone. Contrast to diastereotopic and homotopic. Epimer (R) A diastereomer that differs from a reference molecule in the configuration of exactly one stereocenter. Epimerize (A,M,S) To become an epimer. May happen to: 1. a compound or a sample of compound that changes into its epimer in the course of a reaction (M,S), or 2. a specific stereocenter in a compound that inverts its configuration in the course of a reaction (A). Contrast to racemize. er (S) Same as enantiomeric ratio. Erythro (M) An archaic term describing the relative configuration of two stereocenters in an acyclic compound. If the compound is drawn in a Fischer projection and the major substituents at the two stereocenters are pointed to the same side, the compound is the erythro diastereomer. The modern way of describing the stereochemistry is anti. Contrast to threo. Examples. Gauche (A) The relationship of two substituents, A and D, on two adjacent atoms, B and C, when the A-B-C-D dihedral angle is 60. Geometric isomer (M) Same as diastereomer, but used only to refer to alkenes. Heterochiral (R) Describes the relationship between two enantiomeric chiral molecules. Contrast with homochiral. Homochiral (R) Describes the relationship between two identical chiral molecules. Contrast with heterochiral. (Homochiral) (S) Same as enantiomerically pure.

Homomer (R) A compound or structure that is identical to a reference compound or structure. Homotopic (A) Refers to the relationship between two atoms of the same element or two groups of the same composition in a compound. Homotopic atoms or groups have the same atom-to-atom connections, and either their environments exchange by free rotation about bonds or lone pair inversion, or they can be related by an axis of symmetry in at least one conformation. Homotopic atoms or groups have identical reactivities and spectroscopic properties. Example: Any two H atoms in cyclohexane. Contrast to diastereotopic and enantiotopic. Improper axis of symmetry (M) An imaginary line through a compound. Rotation of the compound by an integral fraction of a circle around this axis (1/2, 1/4, etc.) followed by reflection through a plane perpendicular to this axis brings the compound to superposition on itself. An improper axis of symmetry is represented by Sn, where n is the integral fraction (must be even or 1). The plane of symmetry is an S1 axis, and the center of inversion is an S2 axis. Contrast to proper axis of symmetry. Inversion center (M) Same as center of inversion. Isomer (R) A compound that has the same formula as a reference compound but whose structure (and hence, properties) is not superimposable. Isomers may be either structural isomers or stereoisomers.
L (M)

An archaic term designating the absolute stereochemistry of carbohydrates (sugars) and amino acids. A molecule is L when the arrangement of groups around a stereocenter is the same as the arrangement of groups about the stereocenter of (S)-glyceraldehyde (2,3dihydroxypropanal). In carbohydrates with multiple stereocenters, the stereocenter furthest from the C in the aldehyde or carboxylic acid oxidation state determines the absolute stereochemistry. The amino acids coded by DNA are exclusively L. (But cysteine has the absolute R stereochemistry, whereas all the other amino acids are S.) Not to be confused with levorotatory! Contrast to D. Levorotatory (M,S) Rotates the plane of plane-polarized light counterclockwise, in the ( ) direction. Contrast to dextrorotatory. Like (abbrev. lk) (A) Same as syn, definition 1. Contrast to unlike. Lone pair inversion (A) The "umbrella effect" that enables N to rapidly switch (invert) its configuration. Meso (M) An achiral compound that has chiral configurational diastereomers. Such a compound usually has tetrahedral stereocenters. Mirror plane (M) Same as plane of symmetry. Optical activity (S) The ability to rotate the plane of plane-polarized light. A sample of an enantiomerically enriched chiral compound is usually optically active. Crystals of achiral compounds may also be optically active.

(Optical isomer) (R) Same as enantiomer. Optical rotation (S) The number of degrees, , by which the plane of plane-polarized light is rotated. (Optically pure) (S) Same as enantiomerically pure. (Planar chirality) (M) Describes the shape of certain chiral molecules that lack a tetrahedral stereocenter. These molecules generally contain a flat group, which by itself has only a single plane of symmetry, but whose orbitals are coordinated on one face to a metal. Examples. Contrast to (axial chirality). Plane of symmetry (M) A plane through an achiral object that relates its identical halves. A plane of symmetry is represented by . Same as an S1 improper axis of symmetry. Point group (M) A description of the symmetry of a molecule according to the number and location of axes of symmetry, improper axes of symmetry, and planes of symmetry. Priority A convention used to assign stereochemistry. Group A bound to a stereocenter has higher priority than group B bound to the same stereocenter when the first atom in group A has a higher atomic number than the first atom in group B. If the first atoms have the same atomic number, the second atoms are compared, etc. Prochiral (M) Refers to an achiral compound with a single plane of symmetry. A chemical manipulation that breaks that plane of symmetry will make it chiral. Proper axis of asymmetry (M) Same as axis of symmetry. Prostereogenic (A) Refers to a nonstereogenic atom on which replacement of one substituent with a different one or addition of a new substituent will render the atom stereogenic. R (A) Designates the configuration of a tetrahedral stereocenter. The four groups about the stereocenter are assigned priorities, and the lowest priority group is pointed away from the reader. The stereocenter has the R configuration if the three remaining groups are arranged clockwise from highest to lowest priority. Contrast to S. r (A) Same as R, but refers to a stereocenter in an achiral molecule that has the property that switching two groups attached to this stereocenter generates a configurational diastereomer that is also achiral. Contrast to s. Racemic (S) A sample of a chiral compound that consists of a 1:1 mixture of enantiomers. (Racemic) (A) Refers to a stereocenter in a compound that is a 1:1 mixture of configurations in a sample of that compound. Racemize (A,S)-- To become racemic. May happen to: 1. a sample whose enantiomeric excess decreases in the course of a reaction (S), or 2. a stereocenter whose configurational purity decreases in the course of a reaction (A).

Contrast to epimerize. Resolution (S) The process of separating the enantiomers of a racemic mixture. S (A) Designates the configuration of a tetrahedral stereocenter. The four groups about the stereocenter are assigned priorities, and the lowest priority group is pointed away from the reader. The stereocenter has the S configuration if the three remaining groups are arranged counterclockwise from highest to lowest priority. Contrast to R. s (A) Same as S, but refers to a stereocenter in an achiral molecule that has the property that switching two groups attached to this stereocenter generates a configurational diastereomer that is also achiral. Contrast to r. plane (M) Same as plane of symmetry. Sn axis (n is an integer) (M) Same as improper axis of symmetry. Scalemic (S) Same as enantiomerically enriched. Skeletal isomer (R) Same as structural isomer. Specific rotation ([]) (M) Defined as / l c, where is the measured optical rotation, l is the path length (in cm), and c is the concentration (in g/mL; if the compound is a pure liquid, c = 1). The specific rotation [] is measured at a particular temperature, written as a superscript in C (e.g., []25), and wavelength (usually the sodium D line, 589 nm), written as a subscript (e.g., []D). It is an immutable physical characteristic of a particular compound, like a melting point. Stereocenter (A) Same as stereogenic atom. Stereogenic (A) Describes an atom within a molecule that has the property that switching two groups attached to the atom generates a new stereoisomer of the molecule. Stereogenic atoms may be trigonal, tetrahedral, or have higher coordination numbers. Stereoisomer (R) An isomer of a reference compound or structure that has the same atom-to-atom connections as the reference compound or structure, but has a shape that is nonsuperimposable with it. Contrast to structural isomer. Stereoisomers may be configurational or conformational stereoisomers, and they may be diastereomers or enantiomers. Stereoselective (X) Same as diastereoselective. Stereospecific (X) Same as diastereospecific. Structural isomer (R) An isomer of a reference compound whose atom-to-atom connections are different from the reference compound. Same as skeletal isomer and constitutional isomer. Contrast to stereoisomer. syn (A,X) (1) Describes the relative stereochemistry of two substituents on an acyclic chain in a molecule. If the chain is drawn in horizontal, zigzag fashion and both substituents

are pointing out or in, they are syn. Examples. (2) The relationship of two substituents, A and D, on two adjacent atoms, B and C, when the A-B-C-D dihedral angle is 0. (3) Describes a reaction in which two groups add to the same face of a bond. Contrast to anti. Threo (M) An archaic term describing the relative configuration of two stereocenters in an acyclic compound. If the compound is drawn in a Fischer projection and the major substituents at the two stereocenters are pointed to opposite sides, the compound is the threo diastereomer. The modern way of describing the stereochemistry is syn. Contrast to erythro. Examples. Trans (A,M) (1) Describes the stereochemical relationship of two groups on different C atoms of an alkene. If the XC=CY dihedral angle is 180, the groups are trans. (2) Describes a 1,2-disubstituted alkene whose substituents are trans. (3) Describes the stereochemical relationship of two groups on different tetrahedral C atoms of a single ring in a cyclic compound. Considering the atoms of the ring to be coplanar, if the two groups reside on opposite faces of the plane, the groups are trans. (4) Describes a 1,n-disubstituted cyclic compound with two substituents that are trans to one another. Contrast to cis. Unlike (abbrev. ul) (A) Same as anti, definition 1. Contrast to like. Z (M) Designates the configuration of an alkene. The four substituents of the alkene are assigned priorities. The alkene has the Z configuration when the higher priority substituent on one C is cis to the higher priority substituent on the other C. Contrast to E. Examples.

Classification of stereochemical terms.

Terms referring to: Atoms or groups within a molecule (A) anti asymmetric center (chiral center)* cis configuration diastereotopic enantiotopic epimerize homotopic like lone pair inversion prostereogenic R r Relationship between two compounds or structures (R) anomer atropisomer configurational diastereomer configurational enantiomer configurational stereoisomer conformational diastereomer conformational enantiomer conformational stereoisomer conformer constitutional isomer diastereomer Macroscopic sample of a compound (S) configurational purity configurationally pure dextrorotatory ee enantioenriched enantiomeric excess enantiomeric ratio enantiomerically enriched enantiomerically pure enantiopure epimerize er (homochiral)*

Single molecules (M) achiral achiral compound asymmetric compound (axial chirality)* axis of symmetry Cn axis center of inversion chiral chiral compound cis conformation
D

Reaction (X) anti diastereoselective diastereospecific enantioselective stereoselective stereospecific syn

dextrorotatory E epimerize

(racemic)* racemize S s stereocenter stereogenic syn trans unlike

erythro improper axis of symmetry inversion center

L

levorotatory meso mirror plane (planar chirality)* plane of symmetry prochiral proper axis of symmetry plane Sn axis specific rotation threo trans Z

enantiomer epimer heterochiral homochiral homomer isomer (optical isomer)* skeletal isomer stereoisomer structural isomer

levorotatory optical activity optical rotation (optically pure)* racemic racemize resolution scalemic

*Terms in (parentheses) are improper and should be avoided.

Point Groups
Point groups are a method of classifying the shapes of molecules according to their symmetry elements. Before we can talk about point groups, we need to describe the basic elements of symmetry. These are the proper axis of symmetry (or just axis of symmetry), improper axis of symmetry, plane of symmetry, and inversion center (or point of symmetry).

The proper axis of symmetry is an imaginary line through a compound. Rotation of the compound by an integral fraction of a circle around this axis (1/2, 1/3, etc.) brings the compound to superposition on itself. An axis of symmetry is represented by Cn, where n is the integral fraction. All shapes have at least a C1 axis (the identity axis). The improper axis of symmetry is also an imaginary line through a compound. Rotation of the compound by an integral fraction of a circle around this axis (1/2, 1/4, etc.) followed by reflection through a plane perpendicular to this axis brings the compound to superposition on itself. An improper axis of symmetry is represented by Sn, where n is the integral fraction (n must be even or 1). The plane of symmetry is a plane through a compound that relates its identical halves. A plane of symmetry is represented by and is the same as an S1 axis. The inversion center (or point of symmetry) is an imaginary point in a compound. Reflection of the compound through this point brings the compound to superposition on itself. An inversion center is represented by i and is the same as an S2 axis.

The main classes of point groups are C, D, S, T, O, and I. The first two classes are most common. Each of these classes is subdivided into different point groups.

Compounds in the C class can be Cs, Ci, Cn, Cnv, or Cnh, where n is an integer. o Compounds in the Cs point group have a plane of symmetry and nothing more. o Compounds in the Ci point group have a center of inversion and nothing more. o Compounds in the Cn point group have exactly one Cn axis and nothing more. Compounds in this point group are always chiral.

Examples Compounds in the C1 point group have only the identity axis; in other words, they have no symmetry. Most compounds have C1 symmetry.

Compounds in the Cnv point group have a Cn axis and n planes of symmetry containing the Cn axis. They do not have a plane of symmetry perpendicular to the Cn axis.

Examples. Linear molecules with conical symmetry (CO, ClCCH) are classified in the Cv point group.
o

Compounds in the Cnh point group have a Cn axis and a plane of symmetry perpendicular to the Cn axis.

Examples.

Compounds in the D class contain a Cn axis and n C2 axes perpendicular to it. Compounds in the D class can be Dn, Dnd, or Dnh, where n is an integer. o Compounds in the Dn point group have no additional elements of symmetry. Compounds in this point group are always chiral. This point group is not common.

Examples.

Compounds in the Dnd point group have n planes of symmetry containing the Cn axis. They do not have a plane of symmetry perpendicular to the Cn axis.

Examples.
o

Compounds in the Dnh point group have a plane of symmetry perpendicular to the Cn axis.

Examples. Linear molecules with cylindrical symmetry (N2, HCCH) are classified in the Dh point group.

Compounds in the S class are Sn, where n is an even integer. Compounds in the S class contain a Sn axis plus a Cn/2 axis coinciding with it. Compounds in the T (tetrahedral) class can be T, Td, or Th. Compounds in the T class contain four C3 axes and three C2 axes. o Compounds in the T point group have no additional elements of symmetry. Compounds in this point group are always chiral. This point group is not common. The compound C(XS)4, where XS is a group with a stereocenter with the (S) configuration, is in this point group. o Compounds in the Td point group have three planes of symmetry that contain the C2 axes. This point group is not common. An octasubstituted cubane in which each vertex is alternately substituted with XR and XS is in this point group.

Compounds in the Th point group have six planes of symmetry that contain the C3 axes. Compounds such as CH4 are in this point group.

Compounds in the O (octahedral) and I (icosahedral) classes have even higher symmetry. These point groups are not common. PF6 is in the Oh point group, and C60 is in the Ih point group.

You should also remember that most compounds are conformationally mobile (i.e., constantly changing their shape), and, as a result, the point group of a compound can depend on the time scale. For example, at a very short time scale, 1-propyne (HCCCH3) is in the C3v point group, but at longer time scales, rapid rotation about the CCH3 bond puts it in the Cv point group. Cyclohexane is in the D3d point group at short time scales, when it is in a single chair form, but at longer time scales, at which it is in rapid equilibrium between its two chair forms, it is in the D6h point group.

DRAWING STEREOCHEMICAL STRUCTURES FROM A TO Z Structural diagrams which depict stereochemistry must be prepared with extra care to ensure there is no ambiguity. The ability to proficiently draw and read such structures requires some practice with reference to 3D molecular models. Some simple "do's" and "don'ts" of the art of stereochemical drawing are illustrated below. In general, the molecules are presented in some kind of perspective drawing, based on the idea that the four substituents of a tetrahedral center can be divided into two pairs, laying in mutually perpendicular planes. Most often the center and two of such substituents are shown in the plane of the drawing (i.e. the plane of the drawing surface) and their bonds are depicted as plain lines ( ). Bonds to the other two substituents are shown with different symbols. Bonds to atoms above the plane of the drawing (coming out, toward the viewer) are shown with a bold wedge ( ), with the narrow end of the wedge starting at the stereogenic center. As an alternative bald bar bonds ( ) are used. Bonds to atoms below the plane (going in, away from the viewer) are shown with hash wedges ( ). There are two separate conventions in use. In the American usage the narrow edge points to the central atom, while in the European convention, the wide edge points to the central atom. As an alternative, a bar of hash lines ( ) is used. A broken line ( ) or an open wedge ( ) can also be found in some drawings, but their usage is discouraged. These various presentations are illustrated below on an example of a compound with one stereocenter (in all cases, except where indicated, the same S absolute stereochemistry is shown). The first structure (A) is the favoured presentation, while B shows a rotational variant of A (any rotation within the plane of these drawings is perfectly acceptable). Structure C demonstrates the European convention that has a more consistent perspective view of the wedges. Structure D shows the use of open wedge (not recommended), while structure E illustrates the use of bar bonds, that are commonly employed to designate relative stereochemistry. In our class we will use wedges (A) to indicate absolute stereochemistry (one enantiomer), and bars (E) to designate racemic mixtures (and relative stereochemistry, see below).

In addition to structures with two bonds to the stereocenter in the plane of the drawing (above), some representations may have only one bond in that plane (F and G) and some have none (H and I), as shown below. In structures like F and G or H and I, three or four wedged lines are used to designate the 3D disposition of substituents, respectively. Confusingly, one may often encounter other 3D structures that seem to follow the above conventions, but are in fact different perspective representations. In structures JM the plain bonds () are not in the plane of the drawing. Their 3D disposition is implied by the wedge lines present. For example, in structure J the wedge bond is a mast pole on three legs, and in L and M the plain-line bonds are really going in or out of the plane of the drawing, respectively.. All these arrangements may be visualized in 3D by selecting the appropriate radio-button in the Jmol applet. Of course C, D, and E are in the exact same orientation as A and are not repeated. Note that all the manipulations are just simple rotations of the same molecule. Paying attention to the correct representation of the perspective is crucial. Some incorrect usage of wedge bonds is illustrated in structures N and O. Despite appearances, there is no stereochemical information in such structures. A couple of simple rules can be used to decide adequacy of such drawings: (1) the bold-wedge and the hash-wedge substituents must be on the same side of an imaginary line connecting the plain-line bonded substituents (as in structures A or B), and (2) two bold-wedge subsituents (or two hash-wedge substituents) must be on the opposite sides of an imaginary line connecting the plain-line bonded substituents (as in structures L or M).

Another way to present stereo-centers is with help of Fischer projections which are designed not to employ any wedged lines. In this class we will not cover Fischer projections. The convention used is that all vertical bonds are pointing in, away from the viewer, and all horizontal bonds are pointing out, toward the viewer. Such structures can only have vertical and horizontal bonds on stereocenters, and cannot be rotated by 90 (without a change in stereochemistry). Often, the most oxidized carbon is placed at the top (but other arrangements are acceptable as well). Structure P (above) is the Fischer projection, and it

could be translated into a "wedge" structure H (or structures L or M, above). One has to be careful to distinguish Fischer projections, such as P, from structures where no stereochemistry is explicitly shown, i.e. only plain bonds are used (in such cases 90 angles between drawn bonds should be avoided; see also below). Hydrogen atoms attached to the stereocenter are often not shown explicitly, as is common for skeletal structures in general. If done carefully, the omission does not lead to complications and the stereo information is perfectly readable, but there are instances where ambiguity or loss of stereo information may occur. In general, at the learning stage, it is advisable to show stereocenter hydrogens explicitly.

These structures, labeled with the same letters as their originals above, illustrate clear and unambiguous examples of hydrogens omitted without any loss of stereochemical information. Structure P' is fine as long as it is made clear that it is a Fischer projection. On the other hand, other presentations may be questionable. For example, structure S can be interpreted (correctly) as structure L with hydrogen omitted, but (especially) when drawn by hand it may be interpreted as a poorly drawn structure of R, leading to the opposite 3D information. Despite appearances, structure T does not carry any stereochemical information (the position of hydrogen with its plain-line bond needs to be explicitly specified). If stereochemistry is unspecified, no wedge lines are used, as in structure U. To easily distinguish such situation from Fischer projections, multiple 90 and 180 angles between drawn bonds should be avoided. Alternatively, situations when the stereochemistry is unknown, or a mixture of both enantiomers is present, can be indicated explicitly by a wavy line ( ) as shown in structure W. Similarly, the unspecified stereochemistry of the double bond (E or Z) may be shown by drawing "extended" formulas as in structure X. The wavy line in structure Y is an alternative way to indicate unknown stereochemistry or a mixture of isomers.

For molecules with multiple stereocenters other methods of display are also available. The Newman projection in Z(1) unambiguously defines the absolute stereochemistry on both centers (S,S). Occasionally, a perspective drawing without any wedge or bar bonds is employed as shown in Z(2). This sawhorse representation is a "stretched" version of the Newman projection. When wedges or bars are used, the plain-line bonds should be used to connect the centers, as illustrated for structure Z(3). This approach avoids possible ambiguities as to which wedge bond belongs to which center.

As illustrated by structures Z(4) 'and Z(5) omitting stereocenter's hydrogens (if done properly) often increases the clarity of the presentation. Structure Z(4) with wedge bonds designate absolute stereochemistry, i.e. enantiomerically pure compound with two S centers. In our class, structure Z(5) with bars designates only the relative stereochemistry, i.e. it corresponds to the racemic mixture of (S,S) and (R,R) enantiomers.