Monosubstituted Cyclohexanes

• Substituents can occupy an axial or equatorial

position

• Equatorial is preferred by larger groups. Why?

7.3 Monosubstituted Cyclohexanes. Conformational Analysis 1

 1,3-Diaxial Interactions

• 1,3-Diaxial Interactions: van der Waals repulsions between an

axial substituents on a cycloalkane ring

2
4
 Problems
1) What is the energy cost of a 1,3-diaxial strain
in methylcyclohexane?
2) What about bromocyclohexane?
3) Which of the two molecules above will have
a higher percentage of its molecules in the
equatorial conformation?
 More on Ring Flip

• Note that the “up” substituent remains up and

the “down” substituent remains down after
chair interconversion

7
 Disubstituted Cyclohexanes
1-chloro-2-methylcyclohexane

• Trans: the two groups have an up-down

relationship

• Cis: the two groups have a down-down (or up-

up) relationship

8
 Conformational Analysis
• For disubstituted derivatives, the larger group
will preferentially occupy the equatorial
position

7.4 Disubstituted Cyclohexanes 9

 Problem
1) Which subsituent will most likely occupy the
equatorial position for a greater amount of
time in cis-1-chloro-2-methylcyclohexane?
2) Prove this with calculation.
 Polycyclic Molecules
• Polycyclic molecules: compounds with two or
more rings fused together
– Spirocyclic: two rings that have only a single
common atom
– Bicyclic: two rings that share two or more
common atoms

11
7.6 Bicyclic and Polycyclic Compounds 12
 Classification and Nomenclature
• Fused and bridged bicyclic compounds

7.6 Bicyclic and Polycyclic Compounds 13

 Naming Bicyclic Systems
• Indicate the number of rings using the prefix “bicyclo-”
• Indicate the bridge lengths
– Number of atoms connecting one bridgehead atom to
another (excluding the bridgehead atoms)
– Separate by full periods and place in square brackets.
• Cited in decreasing order of size (e.g. [3.2.1])
• the name of the hydrocarbon indicating the total number
of skeletal atoms
 Problems
• Name the following polycyclic molecules:

Norbornane

Decalin

• If you were just given the IUPAC names for a couple

of bicyclic molecules, how would you tell the
difference between a fused and a bridged variety?
 Cis and Trans Ring Fusion: Decalin

7.6 Bicyclic and Polycyclic Compounds 16

• Each ring in cis-decalin can undergo ring flip

• Ring fusion causes trans-decalin to be

conformationally locked

17
 Ring Fusion with Small Rings
• Bicyclic compounds with small rings are
restricted to cis ring fusion
• Trans fusion would incur too much ring strain

7.6 Bicyclic and Polycyclic Compounds 18

 Steroids

• Organic compounds with 20 carbon,

tetracyclic core
– Variations in substituents dictate biological
activity

7.6 Bicyclic and Polycyclic Compounds 19

 Steroids

• Many consist of all trans-fused rings

– No conformational change
• Many have methyl groups at C-10 and C-13

7.6 Bicyclic and Polycyclic Compounds 20

 Stereochemistry of Cycloalkene Reactions
Addition Reactions

• Syn-addition:

• Anti-addition:

7.9 Stereochemistry of Chemical Reactions 22

 Stereochemistry of Bromine Addition
• Addition of bromine to an alkene is a highly
stereoselective reaction
• Exclusively anti-addition
– Gives all trans products

7.9 Stereochemistry of Chemical Reactions 23

 Stereochemistry of Halohydrin Formation

• Exclusively anti-addition
– Gives all trans products
 Stereochemistry of Hydroboration-Oxidation
• Hydroboration is a stereospecific syn-addition

7.9 Stereochemistry of Chemical Reactions 26

 Stereochemistry of Hydroboration-Oxidation
• The oxidation of organoboranes is a
stereospecific substitution reaction

7.9 Stereochemistry of Chemical Reactions 28

 Stereochemistry of Hydroboration-Oxidation
• The two steps of hydroboration-oxidation
result in net syn-addition of H-OH to the
alkene

• Note that the trans designation of the name

has nothing to do with the way H-OH added

7.9 Stereochemistry of Chemical Reactions 29

 Stereochemistry of Hydrogenation
• Catalytic hydrogenation is a stereospecific syn-
addition

7.9 Stereochemistry of Chemical Reactions 30

 Problem
• Draw the products for the following reactions