Stereochemistry of cyclic

compounds & Chiral

Compounds without
Asymmetric Atom Carbon

Minggu - 6

1
 Conformationally Mobile
Systems
Alkanes and cycloalkanes are conformationally
mobile
rapidly converting from one conformation to another

In order to determine whether a conformationally

mobile molecule is optically active, draw its most
symmetrical conformation
cycloalkane: flat ring
alkane: eclipsed conformation (usually)
 Conformationally Mobile Systems

When drawing cycloalkanes as flat rings:

solid wedge: bond coming up out of the plane of
the paper

dashed wedge: bond going down below the plane

of the paper
Br

Br
 Vertical reflection plane.
Horizontal reflection plane.
Cycloalkanes

Look for reflection

planes!
There are other reflection planes as well. Do you see them?

Based on these planar ring diagrams we observe reflection plane and expect
optical inactivity.
But the actual molecule is not planar !! Examine cyclohexane.

This plane of symmetry (and

two similar ones) are still
present. Achiral. Optically
inactive. The planar diagrams
predicted correctly.
 Chirality of Conformers

If equilibrium exists between two chiral

conformers, molecule is not chiral.
Judge chirality by looking at the most
symmetrical conformer.
Cyclohexane can be considered to be planar, on
average.
 H H
H H
Br Br
H H

Br
Br Br
Br
Nonsuperimposable mirror images, Use planar
but equal energy and interconvertible. approximation.
 1-Bromo-2-chlorocyclopropane

Br R Cl Cl R Br
S S
cis

enantiomers
diastereomers
Br R Br
R S S
trans
Cl Cl

enantiomers
 1,2-Dibromocyclopropane
mirror image identical

Br Br Br Br
cis

meso
diastereomers

Br Br
trans
Br Br

enantiomers
 1-Bromo-2-chlorocyclohexane

Br Cl Cl Br cis

enantiomers
diastereomers

Br Br trans

Cl Cl
enantiomers
 As long as any one conformer of a compound has a
plane of symmetry, the compound will be achiral

plane of
symmetry
plane of
symmetry
Conformational Mobility of Cyclohexane

Hax
Heq

Heq

Hax

- Energy barrier of interconversion; 45 kJ/mol (10.8 kcal/mol)

(20 kcal/mol available at 25 )
- Hax and Heq are indistinguishable
 Substituted cyclohexanes
The planar diagram predicts achiral and
optically inactive. But again we know the
cis structure is not planar.

Mirror
objects!!

But recall the chair interconversion.

This is a chiral structure Earlier we showed that the two structures have the
and would be expected same energy. Rapid interconversion. 50:50 mixture.
to be optically active!! Racemic mixture. Optically Inactive. Planar
structure predicted correctly
trans No mirror planes.
Predicted to be
chiral,
optically
active.
Enantiomer.
Ring Flips??????

R,R trans 1,2 dimethylcyclohexane R,R

Each structure is chiral. Not mirror images! Not the same! Present in different
amounts. Optically active!
 Stereoisomerism of Cyclic Compounds
1,4-dimethylcyclohexane
Neither the cis not trans isomers is optically active
Each has a plane of symmetry

15
 1,3-disubstituted

Cis
Symmetry plane
Meso compound
CH3 CH3

CH3 CH3
 1,3-disubstituted

Trans
No symmetry plane
Therefore enantiomers

CH3 CH3

CH3 CH3
 1,3-dimethylcyclohexane
The trans and cis compounds each have
two stereogenic centers
The trans compound exists as a pair of
enantiomers
 Br

CH
CH33 Diastereomers
H
2 asymmetric
H carbons CH3
no internal plane of symmetry H *
Draw and check mirror image
* H
Br
Draw and check mirror image

CH
CH33 H3C
HH H Not superimposable
HH Chiral
H
Br
Br Br
 Br

Diastereomers
CH3
H *
* H
Br
Naming:
1-bromo-3-methylcyclohexane.

Specify (R) and (S) configuration for each asymmetric carbon:

(1R, 3R)-1-bromo-3-methylcyclohexane
 Diastereomers
Example: Is the following compound chiral?

H
CH3
H
Br

Br
H
H3C
H
 Diastereomers
Redraw it in its most symmetrical conformation.

H CH3 CH3
CH3 Br
H H Br
Br
H H or
Br
H H
H3C Br Br
H CH3
H H CH3
4 asymmetric carbons, no internal mirror plane of symmetry
may be
CHchiral
3
CH3
HmirrorBr H

Br draw and check image
 Diastereomers
CH CH3
CH3 3
Br Br
Br

Br
Br Br
CH CH3
CH3 3

H These structures
H are SUPERIMPOSABLE!
Not chiral!
CH3
H
BrBr
H3C
 Chirality at Nitrogen, Phosphorus, and
Sulfur
N, P, S commonly found in organic compounds, and
can have chirality centers
Trivalent nitrogen is tetrahedral
Does not form a chirality center since it rapidly flips
Individual enantiomers cannot be isolated
Amine Inversion
 Also applies to phosphorus but it flips more slowly
( R)-methyl methyl(phenyl)- ( S)-methyl (phenyl)propyl-
phosphinate phosphineoxide

( S)-N-ethyl-N- ( R)-methyl phenylsulfoxide

methylaniline-N-oxide
Find configuration these compounds:
Chiral Compounds w/o Asymmetric Atom
Carbon

Although most chiral compounds have at least

one asymmetric atom, there are some chiral
compounds that have zero asymmetric atoms:
Allenes
conformation enantiomers
 Chiral Molecules that Do Not Possess a
Tetrahedral Atom with Four Different Groups
Atropoisomer: conformational isomers that are stable
 Allenes:
compounds containing a C=C=C unit
central carbon is sp hybridized
linear
 Another possiblility of enantiomers

-Some special molecules:

a. pentadiene

H3C C H3 H3C C H3
C C C C C C
H H
H H
 Mirror planes
1,2-dichloroallene (1,3-dicholoropropa-1,2-diene)
( Ra)-1,3-dicholoroallene
( Ra)-1,3-dicholoroallene
 Conformational enantiomers:
compounds that are so bulky or so highly strained that they
cannot easily confert from one chiral conformation to the
mirror-image conformation
locked into one conformation
Binaphthyls

S-configuration
S-configuration
 do not occur in nature
 Spirans compound
Spirane from Latin Spira meaning twist.
A spiro atom is one which is the sole common
member of two rings.