Conformations of Cycloalkanes

1
 Angle and Torsional Strain
• Bond-line structures of cycloalkanes shown below depict the structures as being
planar. Internal bond angles are calculated from geometry.

• We know that conformational isomers of non-cyclic alkanes exist due to the

rotation of a σ bond & some conformers are lower in energy than others.
• Cycloalkanes too have different stabilities. Stabilities depend on the ring size
and some cycloalkanes can adopt non-planar shapes and conformations
through bond rotation in order to reduce their energy, by reducing:
a. Angle Strain: Strain due to a bond angle that is either less than or
greater than the ideal bond angle of an sp 3 carbon (109.5º)
b. Torsional Strain: Strain due to eclipsing bonds on adjacent atoms

Image and text accessed on Sept. 28, 2022: Credit:

“Ring Strain and the Structure of Cycloalkanes”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Bookshelves/Orga nic_Chemistry /Map% 3A_Org anic_Chemist ry_(Vollhard t_and_Scho re)/ 04._Cycloalkanes /4.2% 3A_Ring__Strain_ _and__ the_Struc ture_ of_Cycloalkanes
Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks: https://kpu.pressbooks.pub/organicchemistry /chapte r/4- 2-rela tive-stability- of-cycloalkan es/
2
 Angle Strain: Cyclopropane
• Cyclopropane is a planar molecule with all C-C-C bond angles 60°.
 much less than the ideal 109.5° bond angles in an sp3 carbon
This results in a large angle strain.

109.5°

60°

• An end-to-end orbital overlap of sp3-sp3

Good overlap
orbital results in effective overlap and a
strong σ bond.
Poor overlap • Geometry of the 3-membered ring results in
poor orbital overlap & weak bonding.
3
Image and text accessed on Sept. 28, 2022: Credit: Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks: https://kpu.pressbooks.pub/organicchemistry/chapter/4-2-relative-stability-of-cycloalkanes/
 Torsional Strain: Cyclopropane
• The ring is constrained preventing bond rotation
 All 6 C-H bonds in this molecule are eclipsed!

Look this way

Unfavorable eclipsed
hydrogens

4
Image adapted and text accessed on Sept. 28, 2022: Credit: Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks : https://kpu.pressbooks.pub/organicchemistry/chapter/4 -2-relative-stability -of-cycloalkanes/
 Strain in Cyclopropane: C3H6

60°

1. Angle strain: the C-C-C bond angles are compressed from 109.5° in an
sp3 carbon to 60° in cyclopropane.
2. Torsional strain: there are 6 eclipsed hydrogen interactions.

 Strain energy is about 115 kJ/mol

 Cyclopropane is very reactive undergoing ring opening reactions in
order to relieve this strain!

Image adapted and text accessed on Sept. 28, 2022: Credit:

“Conformations of Cycloalkanes:, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Bookshelves/Organic_Che mistry/O rganic_Che mistry_( Libre Texts)/ 04% 3A_Organic_Co mpounds -_Cycloalkanes_ and_th eir_Stere ochemist ry/4.04% 3A_Confo rmatio ns_of_Cycloalkan es
Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks: https://kpu.pressbooks.pub/organicchemistry /chapte r/4- 2-rela tive-stability- of-cycloalkan es/ 5
 Cyclobutane puckers to relieve torsional strain
Planar conformation
• A planar cyclobutane with all carbons coplanar would have 8 eclipsing
hydrogen interactions.

90°

Look this way

Puckered conformation

• Unlike cyclopropane, cyclobutane has a way to reduce torsional strain by

allowing the ring to pucker out of plane. Now H’s not quite eclipsed.

Im a g e ac ce sse d on Se pt. 2 8, 20 22 : Cred it : Look this way 6

Be n j a h -b mm2 7, Pu bl i c do mai n, vi a Wi ki me di a Co mmon s: https :/ /com mon s.wik im ed ia .o rg/wi ki /F i le :Cy cl ob utan e-b uc kl ed -3 D-ba l s.p ng
“Co n fo rm ati on o f Cy cl oa lk an es”, CCBY-NC-SA, vi a Li bre Te xts: h t p s:// ch em.l ib retex ts .o rg/Cou rse s/Ath ab asc a_ Uni ve rsi ty /Ch emi stry_ 35 0% 3A_Org an ic _Ch emi stry_ I/ 0 4%3 A_Org an ic _Co mpo un ds -_ Cyc lo al ka ne s_ an d_ th ei r_Stere och em is try/4 .0 4% 3A_Co nfo rm atio ns _o f_ Cyc lo al ka ne s
Be n j a h -b mm2 7, Pu bl i c do mai n, vi a Wi ki me di a Co mmon s: h t p s:// co mmo ns.wi ki med i a.org /wi ki /Fi l e:Cycl o bu ta ne -3D-ba l ls .p ng
 Torsional Strain: Cyclobutane

5.9 kJ/mol

The position of the out of plane carbon can be shifted from one carbon to the
next. This requires only 5.9 kJ/mol in energy (Recall: At room temperature,
molecules have enough kinetic energy to get over barriers as high as 83.7
kJ/mol).

 Through constant motion one carbon is always out of plane

Images accessed on Sept. 28, 2022: Credit: Smokefoot, Public domain, via Wikimedia Commons ; https://commons.wikimedia.org/wiki/File :CyclobutaneConf2.png
7
 Strain in Cyclobutane: C4H8
Puckered conformation

1. Angle strain: Upon trying to relieve some torsional strain, bond angles
decrease from 90º (planar) to 88º (puckered) thereby slightly increasing
angle strain. 88⁰ is far from the bond angles of an ideal sp3 carbon
(109.5⁰).
2. Torsional strain: It is still present but not quite eclipsed in the puckered
conformation as it would be in the planar conformation.

 The puckered conformation is the lowest energy conformation.

 Strain energy is about 110 kJ/mol

8
Image and text accessed on Sept. 28, 2022: Credit: Conformations of Cycloalkanes:, CC BY-NC-SA, via LibreTexts: https://chem.libretexts.org/Courses/Athabasca_University/Chemistry_350%3 A_Organic_Chemistry_I /04%3 A_Organic_Compounds -_Cycloalkanes_and_their_Stereochemistry/4 .04%3 A_Confor mations_of_Cycloalkanes
 Cyclopentane: C5H10
Planar conformation
• A planar cyclopentane with all carbons coplanar has very little angle strain with
bond angles 108º. It however has a lot of torsional strain with 10 eclipsing
hydrogen interactions.

108°

Envelope conformation
• Thus, cyclopentane distorts in a similar way as cyclobutane by puckering
(adopt envelope conformation) in order to reduce some of the torsional
strain.

Look
this
way

Im a g e an d tex t ac ce sse d on Se pt. 2 8, 20 22 : Cred it :

Ed g a r1 8 1 , Pub li c d oma in , v ia Wi ki med ia Commo ns : https://c omm on s.wik ime di a .o rg/wik i/ Fil e :Cy cl op en ta ne 3D.pn g
9
J y n to , CC0, v ia Wi ki med i a Comm on s: https :/ /com mon s.wik im ed ia .o rg/wi ki /F i le :Cy cl op en ta ne -3D-b al ls .p ng
Co n fo rm a ti on s of Cycl o al ka ne s:, CC BY-NC-SA, vi a L ib reTex ts : http s://c he m.l i bre te xts.org /Co urse s/Ath ab as ca _Un iv ersi ty/Che mis try _3 50 %3A_ Orga ni c_ Che mis try _I/0 4% 3A_ Org an i c_Co mp ou nd s-_Cy cl oa lk an es_ an d_ the ir_ Ste re oc he mi stry /4 .04 %3A_ Con fo rmati on s_ of_Cy cl oa lk an es
 Cyclopentane pseudorotation
• In the envelope conformation four carbons are in a plane and one is
either above or below the plane
• The ‘flap’ moves around the ring (pseudorotation), so that all 5 carbons
have a chance of being at the top of the flap! One carbon is always out of
plane.

Envelope conformation

Pull 1 down

• Carbons 2, 3, 4, & 5 • Carbon 1, 3, 4, & 5

in same plane in same plane
• Carbon 1 is up • Carbon 2 is down
10
Image accessed on Sept. 28, 2022: Credit: “Conformation of Cycloalkanes”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Courses/Athabasca_University/Chemistry_350%3A_Organic_Chemis try_I/04 %3A_Organic_Compounds -_Cycloalkanes_and_their_Stereochemis try/4.04 %3A_Con format ions_of_Cycloalkanes
 Strain in Cyclopentane: C5H10
Envelope conformation

1. Angle strain: Upon trying to relieve some torsional strain, bond angles
decrease from 108º (planar) to 107º (envelope) thereby slightly increasing
angle strain. 107⁰ is less than the bond angles of an ideal sp3 carbon
(109.5⁰).

2. Torsional strain: It is still present but less. Atoms eclipsed at the bottom of
the envelope, but almost staggered at the flap and sides.

 The envelope conformation is the lowest energy conformation.

 Strain energy is 26 kJ/mol
11
Image and text accessed on Sept. 28, 2022: Credit: “Conformation of Cycloalkanes”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Courses/Athabasca_University/Chemistry_350%3 A_Organic_Chemistry_I /04%3 A_Organic_Compounds -_Cycloalkanes_and_their_Stereochemistry/4 .04%3 A_Confor mations_of_Cycloalkanes
 Cyclohexane: C6H12
Planar conformation
• A planar cyclohexane with all carbons coplanar would have bond angles of
120º, larger than those of an ideal sp 3 carbon (109.5⁰). It would thus have a
lot of angle strain and a lot of torsional strain with 12 eclipsing hydrogen
interactions.

Look this way

Chair conformation
• So, cyclohexane also puckers, but unlike cyclopentane with 1 flap,
cyclohexane has 2 flaps. By adopting a chair conformation, it can eliminate
torsional strain by having all adjacent groups staggered.

Look
this way

12
Text adapted on Dec. 27, 2022: Credit: “Conformations of Cyclohexane”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Courses/Athabasca_University/Chemistry_350%3 A_Organic_Chemistry_I /04%3 A_Organic_Compounds -_Cycloalkanes_and_their_Stereochemistry/4 .05%3 A_Confor mations_of_Cyclohexane
 Strain Cyclohexane
Pull 4 up
5 6

4 120° 1

3 2
Planar Chair
Pull 1 down

1. Angle strain: There is NO angle strain in the chair conformation! Bond

angles are ~ 109.5°
2. Torsional strain: There is NO torsional strain in the chair conformation!
All eclipsing interactions are eliminated. Hydrogens on adjacent
carbons are staggered.

 Chair conformation is the lowest energy conformation.

 Strain energy is 0 kJ/mol

13
Image and text adapted and accessed on Sept. 28, 2022: Credit: Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks : https://kpu.pressbooks.pub/organicchemistry/chapter/4 -3-conformation-analysis -of-cyclohexane-and-substituted-cyclohexanes /
 Cyclohexane Chair

Look this
way

• Chair conformation: the most stable puckered conformation of a

cyclohexane ring
• All bond angles are ~ 109.5°
• All groups on adjacent carbons are staggered.
• No torsional strain.

14
Image adapted and text adapted and accessed on Sept. 28, 2022: Credit: Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Press books : https://kpu.pressbooks.pub/organicchemistry/chapter/4 -3-conformation-analysis -of-cyclohexane-and-substituted-cyclohexanes /
 6-membered rings
6-membered rings are the most encountered in nature….
 Why?
 It is an unstrained molecule

For example: Diamond

• Diamond consists of tetrahedral carbon atoms covalently bonded to
each other in a three-dimensional network of chair conformations.
• Results in a stable, extraordinarily rigid and hard structure.
15
 Quantify Strain: Heat of combustion cycloalkanes
Molecule Energy per CH2 group
(kcal/mol)
cyclopropane 156.2
Hydrocarbon + O2
 CO2 + H2O + heat cyclobutane 153.6
cyclopentane 148.3
1 kcal/mol  4.2 kJ/mol
cyclohexane 147.0
cycloheptane 147.9
cyclooctane 148.2
cyclodecane 148.1
n-alkane 147.0
• The more energy released per CH2, upon combustion of the
hydrocarbon, the higher the energy of the starting compound
• Higher energy relates to lower stability (or ring strain)
• Thus more energy released, the lower the stability of the molecule
• Cyclohexane more stable than cyclopropane and cyclobutane.
• Heat of combustion per CH2 is lowest for cyclohexane equivalent to an n-
alkane indicating a low energy stable ring with no strain!
Da ta a n d te xt ac ce sse d on Se pt. 2 9, 20 22 : Cred it : “Sta bi l it y of Cycl o al ka ne s – Rin g Stra i n”, CC BY-NC-SA, v ia L i breTe xts: https :/ /che m.li b re texts.o rg /Bo ok sh el ve s/Org an i c_Ch em is try/Orga ni c_ Che mi stry_(L ib reTex ts )/0 4% 3A_Org an ic _Co mpo un ds -_Cyc lo al ka ne s_ an d_ th ei r_Stere oc he mis try /4 .0 3% 3A_ Sta bi li ty_ of_Cy cl oa lk an es_ -_Ri ng _Strai n
16
 In class problem

1. Which one(s) the following cycloalkane rings puckers to reduce

torsional strain?
2. Which one would have greatest amount of heat released upon
combustion?

A. Cyclohexane
B. Cyclopropane
C. Cyclobutane

17
 Ring Strain: Effect on Reactivity
Consider the Ni-catalyzed reaction with H2 to generate a completely
saturated linear alkane
H2/Ni
CH3CH3
20° C

H2/Ni
CH3CH2CH3
120° C

H2/Ni
CH3CH2CH2CH3
200° C

H2/Ni
or no reaction
200° C

 Cyclopentane and cyclohexane are stable structures compared to

cyclopropane and cyclobutane under the same conditions. 18
 Cyclohexane Chair
• There are two types of substituents in a cyclohexane “chair”

1. Axial
• 6 vertical
positions; 3 above
and 3 below the
plane of the ring
2. Equatorial
• 6 positions that lie
in a ring outside
the carbon
skeleton
(periphery) and
are roughly in the
plane of the
molecule
19
Im a g e an d tex t ac ce sse d on Se pt. 3 0, 20 22 : Cred it :
“Ax ia l a nd Equa to rial Bonds in Cyc lo hex ane” , CC BY-NC-SA, v ia LibreTex ts: https :// c he m.li brete xts.org/Book she lv es /Orga nic_ Chemis try /Orga nic _Chem is try_ (L ibre Tex ts )/0 4% 3A_ Orga nic _Compounds-_Cy cloalka nes _a nd_their_ Ste reoche mistry/4 .0 6% 3A_ Axial_a nd_ Equatorial_Bonds _in_Cy clohe xa ne
Be n j a h -b mm2 7, Pu bl i c do mai n, vi a Wi ki me di a Co mmon s: h t p s:// co mmo ns.wi ki med i a.org/wi ki /Fi l e:Cycl o he xan e-c ha ir-co lo ur-co de d-3 D-ba l s.pn g
 Cyclohexane Ring

Axial hydrogens equatorial hydrogens

Overall, there are:

• 6 hydrogens pointing up
• 6 hydrogens pointing
down

20
 Cyclohexane Chair: How to Draw It

1. draw 2. add a 3. add axial hydrogens at the

offset triangular flap points, alternating
parallel on top and straight up and straight
lines bottom down
• ensure each • If the points on the
line drawn is triangular flap points up,
parallel to one the hydrogen is up
other line • If the points on the
triangular flap points down,
the hydrogen points down

Image and text accessed and modified on Sept. 30, 2022: Credit:
David Klein, Organic Chemistry 4 th edition, John Wiley & Sons, 2021
Todd:Chem3x11 ToddL2, CC BY 3.0, via OpenWetWare: https ://openwetware.org/wiki/Todd:Chem3x11_ToddL2
Tim Soderberg, “Conformation of cyclic organic molecules”, CC BY-NC-SA, via LibreTexts: https://chem.libretexts.org/Under_Constr uction/Purgatory/ Book%3 A_Organic_Chemistry_with_a_ Biological_E mphasis_(Soderberg)/Chapter_03 %3A_Confor mations_and_ Stereochemi stry/03 .2 %3A_Confor mations_o f_cyclic_organic_molecules
21
 Cyclohexane Chair: How to Draw It
4. Add the equatorial hydrogens
such that the carbons looks
tetrahedral

• If the axial hydrogen is pointing

up, the equatorial hydrogen
should point slightly
downwards.
• If the axial hydrogen is pointing
down, the equatorial hydrogen
should point slightly upwards
• Thus alternate the equatorial
hydrogens with slightly
pointing up with slightly
pointing down
• Note that the equatorial bonds
are parallel to a C-C bond one
bond away.
Image and text accessed and modified on Sept. 30, 2022: Credit:
David Klein, Organic Chemistry 4th edition, John Wiley & Sons, 2021
Todd:Chem3x11 ToddL2, CC BY 3.0, via OpenWetWare: https://openwetware.org/wiki/Todd:Chem3x11_ Todd L2
22
Tim Soderberg, “Conformation of cyclic organic molecules”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Under_Const ruction/Pu rgato ry/Book% 3A_Organic_Che mistry_with_ a_Biological_Emphasis_(Sod erbe rg)/Cha pter_ 03% 3A_Conform ations_an d_Stereoc hemi stry /03.2% 3A_Confo rmations _of_cyclic_or ganic_molec ules
On your own
How to Draw a Cyclohexane Chair: Alternate Method
1. Draw a zig-zag (4 bonds in length)

2. Draw another zig-zag parallel and

underneath the first one, positioned
one bond length to the left or right
3. Connect the two zig-zags with two
parallel lines

4. Add a H at the end of those 4

horizontal bonds. Add the two
remaining equatorial bonds to
hydrogens (6 equatorial positions).
5. Add 6 axial bonds at the points, 3 up
and 3 down (alternating around
the ring). Add a H at the end of
those bonds.
23
 Chair to chair conversion
• There is two chair conformations. To easily see them, build a
model and mechanically twist the two carbons shown below.
• In nature, the chair proceeds through various conformations before
converting from one chair conformation to another (… see later on)

Twist this carbon up

Twist this carbon down

24
Image accessed and text adapted on Sept. 30, 2022: Credit: Tim Soderberg, “Conformation of cyclic organic molecules”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Under_Construction/Purgatory/Book %3A_Organic_Chem istry_with_a_Bio logical_E mphasis_(Soderberg)/C hapter_03%3 A_Conforma tions_and_S tereochemistry/03 .2%3 A_Conforma tions_of_cyclic_organic_molecules
 Chair to Chair Conversion of cyclohexane

Axial up
Equatorial
down
Equatorial
Ring Flip up
Axial
down

• These are two equivalent chair conformations in equilibrium and

cyclohexane rapidly rotates between them through a ‘ring flip’.
• After a ring flip:
 Axial substituents become equatorial substituents
 Equatorial substituents become axial substituents
 Substituents that were pointing up remain pointing up
 Substituents that were pointing down remain pointing down
Image and tex t ac c es s ed on Sept. 30, 2022: Credit:
“Ring flip" des c ribes the rapid equilibrium of c y c lohex ane rings between the two c hairc onformations ”, CC BY-NC-SA, v ia LibreTex ts: Map%3A_Organic _Chemis try _(Vollhardt_and_Sc hore)/04._Cy c loalk anes /4.3%3A_Cy c lohex ane%3A_ A_S train-Free_Cy c loalk ane
Tim Soderberg, “Conformation of c y c lic organic molec ules ”, CC BY-NC-SA, v ia LibreTex ts: https ://c hem.libretex ts .org/Under_Cons truc tion/Purga tory /Book %3A_Organic _Chemis try _with_a_Biolog ic al_Emphas is _(Soderberg)/Chap ter_03%3 A_Conforma tions _and_S tereoc hemis try /03.2 %3 A_Conforma tions _of_c y c lic _organic _molec ules
25
 In class problem

State whether the Cl, Br, and CH3 substituents are in an axial or equatorial position?

26
Problem and image taken and the text slightly adapted on Dec. 10, 2022: Credit: “Cyclohexane: A Str ain-Fr ee Cycloalkane”, CC BY-NC-SA, via Libr eTexts: https://chem .libr etexts. or g/Bo oksh elves/ Or gani c_Chem istr y/ Map% 3A_Or ga nic_C hem istr y_(Vol lhar d t_an d_Sch or e)/04 ._Cycl oalka nes/4 .3% 3A_Cyclo hexa ne% 3A_A_Str ain- Fr ee_Cycl oalka ne
 Chair to chair conversion

Equatorial
hydrogens

27
 Chair to chair conversion

Axial
hydrogens
(top)

28
 Chair to chair conversion

Axial
hydrogens
(top and
bottom)

29
 Ring Flip

equatorial

30
Ring Flip

31
Ring Flip

32
Ring Flip

33
Ring Flip

34
Ring Flip

35
Ring Flip

36
Ring Flip

37
Ring Flip

38
Ring Flip

39
 Ring Flip

axial

40
Cyclohexane Ring Flip: Compare the
conformation of cyclohexane with ethane

Ethane:
Hydrogens
are staggered

41
Ring Flip:

Cyclohexane:
hydrogens
are
staggered

42
Ring Flip:

hydrogens
are
staggered

Chair conformation 43
Ring Flip:

44
Ring Flip:

45
Ring Flip:

46
Ring Flip:

hydrogens
are eclipsed

Boat Conformation 47
Ring Flip:

48
Ring Flip:

49
Ring Flip:

50
Ring Flip:

51
Ring Flip:

hydrogens
are
staggered

Chair conformation 52
Ring Flip:

All carbon –
hydrogen
bonds are
staggered

Chair conformation 53
 Boat Conformation: Torsional Strain
• In the course of ring-flipping, cyclohexane proceeds through a boat
conformation and eclipsed arrangements of hydrogens.

Boat conformation
 Less stable than a chair conformation by ~30 kJ/mol

H
Look this
way

Torsional Strain: 4 pairs of Eclipsing hydrogens

at bottom of boat

Image and text accessed on Sept. 30, 2022: Credit:

“Cyclohexane: A Strain-free Cycloalkane”, CC BY-NC-SA’ via LibreTexts: https://chem.libretexts.org/Courses/Kenyon_College/Ch emistry_ 231_an d_232_ -_Kenyon_Colleg e_(Ge tzler_Hoff erbe rth_an d_Hunsen )/4% 3A_Cycloalkanes/4.3% 3A_Cyclohexan e% 3A_A_Strain-Fr ee_Cycloalkane
Tim Soderberg, “Conformation of cyclic organic molecules”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Under_Const ruction/Pu rgato ry/Book% 3A_Organic_Che mistry_with_ a_Biological_Emphasis_(Sod erbe rg)/C ha pter_ 03% 3A_Conform ations_an d_Stereoc hemistry /03.2% 3A_Confo rmations _of_cyclic_or ganic_molec ules
54
 Boat Conformation: Steric Strain

Flag ship Hydrogens

• Steric strain: Strain due “to the repulsive interactions of atoms trying to
occupy the same space”
• In the boat conformation there is steric crowding between the two flag-ship
hydrogens
 ‘they are too close for comfort’

Image and text accessed on Sept. 30, 2022: Credit:

55
“Ring Strain and the Structure of Cycloalkanes”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Courses/Kenyon_Colleg e/Chemist ry_231_ and_23 2_-_Kenyo n_College_( Getzler_Ho fferb erth_ and_Hunse n)/4% 3A_Cycloalkanes/4 .2% 3A_Ring__Strain__a nd__th e_Structu re_of _Cycloalkanes
Tim Soderberg, “Conformation of cyclic organic molecules”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Under_Const ruction/Pu rgato ry/Book% 3A_Organic_Che mistry_with_ a_Biological_Emphasis_(Sod erbe rg)/C ha pter_ 03% 3A_Conform ations_an d_Stereoc hemistry /03.2% 3A_Confo rmations _of_cyclic_or ganic_molec ules
 Twist-Boat conformation
The energetics of the twist-boat conformation lies somewhere between a
chair and a boat:
The twist-boat can relieve some of the strain of the boat: flagpole
hydrogens farther apart, hydrogens more staggered (less fully eclipsed).
• ~ 23 kJ/mol less stable than the chair conformation.
• ~ 7 kJ/mol more stable than the boat conformation.

Image and text accessed and only slightly modified on Sept. 30, 2022: Credit:
56
“Cyclohexane: A Strain-free Cycloalkane”, CC BY-NC-SA’ via LibreTexts: https://chem.libretexts.org/Courses/Kenyon_College/Ch emistry_ 231_an d_232_ -_Kenyon_Colleg e_(Ge tzler_Hoff erbe rth_an d_Hunsen )/4% 3A_Cycloalkanes/4.3% 3A_Cyclohexan e% 3A_A_Strain-Fr ee_Cycloalkane
Keministi, Public domain, via Wikimedia Commons: https://commons.wikimedia.org/wiki/File:Cyclohexane_ring _flip_and_ relative_co nfor mation_e nergies.sv g
 Half-chair conformation
The half-chair conformation is the highest energy conformation:
It has only 1 carbon out of the plane of the ring.
It has a lot of ring strain (recall planar bond angles are 120 º) and it has a
lot of eclipsing interactions.
• ~ 45 kJ/mol less stable than the chair conformation.

Image and text accessed on Sept. 30, 2022: Credit:

57
“Cyclohexane: A Strain-free Cycloalkane”, CC BY-NC-SA’ via LibreTexts: https://chem.libretexts.org/Courses/Kenyon_College/Ch emistry_ 231_an d_232_ -_Kenyon_Colleg e_(Ge tzler_Hoff erbe rth_an d_Hunsen )/4% 3A_Cycloalkanes/4.3% 3A_Cyclohexan e% 3A_A_Strain-Fr ee_Cycloalkane
Keministi, Public domain, via Wikimedia Commons: https://commons.wikimedia.org/wiki/File:Cyclohexane_ring _flip_and_ relative_co nfor mation_e nergies.sv g
 Chair to Chair Conversion: Energetics
Half-chair Half-chair

45
kJ/mol

Boat

30
23
Chair Chair
Twist-Boat Twist-Boat

Progress 

• The energy changes along with the conformation

• The chair is the most stable conformation because of no steric nor torsional
strain!
Image and text accessed on Sept. 30, 2022: Credit:
“Cyclohexane: A Strain-free Cycloalkane”, CC BY-NC-SA’ via LibreTexts: https://chem.libretexts.org/Courses/Kenyon_College/Ch emistry_ 231_an d_232_ -_Kenyon_Colleg e_(Ge tzler_Hoff erbe rth_an d_Hunsen )/4% 3A_Cycloalkanes/4.3% 3A_Cyclohexan e% 3A_A_Strain-Fr ee_Cycloalkane
Keministi, Public domain, via Wikimedia Commons: https://commons.wikimedia.org/wiki/File:Cyclohexane_ring _flip_and_ relative_co nfor mation_e nergies.sv g
58
 In class problem

With respect to the four conformations of cyclohexane (half chair, chair,

boat, and twist boat), the order of increasing ring strain is …..

A. boat < twist-boat < half-chair < chair

B. chair < twist-boat < boat < half-chair
C. boat < half-chair < half-boat < chair
D. chair < boat < half-chair < half-boat
E. half-chair < chair < half-boat < boat

59
Problem taken and slightly adapted on Sept. 30, 2022: Credit: Wayne Morsch, “Cyclohexane”, CC BY NC -SA, via LibreTexts: https://chem.libretexts.org/Courses/University_ of_Illinois_Springfield /UIS% 3A_CHE_267_-_Organic_Ch emistry_ I_(M orsch) /Chapte rs/Chapte r_04% 3A_Alkanes/3.1 1% 3A_Cyclohexane
 Chair to chair conversion

• The largest (rate-limiting) energy barrier for chair-to-chair

interconversion requires an energy difference of ~ 45 kJ/mol (10.7
kcal/mol).

• Recall: At room temperature, molecules have enough kinetic energy

to get over barriers as high as 83.7 kJ/mol (20 kcal/mol).
 at room temperature interconversion between chair
conformations occurs rapidly.
 There is rapid interconversion of axial and equatorial hydrogen
atoms.

• But cyclohexane, prefers to exist in the lowest energy conformation

 99.9% of all cyclohexane exists in the chair conformation at room
temperature!

60
Text accessed and adapted slightly on Sept. 30, 2022: Credit: John D. Roberts and Marjorie C. Caserio, “Conformations of Cycloalkanes”, CC BY NC-SA, via LibreTexts: https://chem.libretexts.org/Bookshelves/Orga nic_Chemistry /Book% 3A_Basic_Principles_of_Orga nic_Chemistry _(Robe rts_and _Caseri o) /12% 3A_Cycloalkanes_Cycloalkenes_ and_Cycloalkynes/ 12.03% 3A_Confo rmations _of_Cycloalkanes
Look at specific interactions more
closely

61
Chair Conformer

62
 Chair Conformer: 1,3-Diaxial Interaction

1,3 Diaxial
interaction:
Steric interaction
where one
substituent axial
on carbon 1
interacts with 1
another
substituent axial
on the same side 2 3
of the ring at
position 3 or 5.
In this case,
substituents on
carbon 1 and 3
interact.

63
Text accessed on Oct. 1, 2022: Credit: Layne Morsch, “Substituted Cycloalkanes”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Courses/University_of_Illinois_Spring field /UI S%3 A_CHE_267_ -_Organic_Chemistry_I_( Morsch)/Chapters /Chapter_04%3 A_Alkanes/3 .12%3 A_Subs titu ted_Cycloalkanes
 Chair Conformer: 1,3-Diaxial Interaction

Two unfavorable
1,3 diaxial
interactions

Between:
1. Substituents 1
on carbons 1
and 3
2. Substituents 2 3
on carbons 1 6
and 5 5
4

64
 Boat Conformer: “Flagpole” Positions

The two carbon

atoms on the boat
conformation that lie
above the plane
defined by the other
four carbon atoms
are called the
‘flagpole’ positions.

65
 Boat Conformer: 1,4-Diaxial Interaction

The hydrogen atoms on

the ‘flagpole’ positions
are close enough for an
unfavorable repulsive
interaction: a 1,4-diaxial 1 4
interaction.

2
3

66
 Boat Conformer: Review

The boat conformation is less stable

than the chair conformation because
of:

I. unfavorable eclipsed
conformations of the carbon-
hydrogen bonds

II. unfavorable 1,4-diaxial

interaction of the hydrogen
atoms on the ‘flagpole’ positions
of the molecule.
Space-filling boat conformation

67
 Energy difference and Equilibria

G° = ∆𝐺 ° 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∆𝐺 ° 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

= −𝑅𝑇𝑙𝑛𝐾𝑒𝑞
Or
G° = −2.303𝑅𝑇𝑙𝑜𝑔𝐾𝑒𝑞

Where;
G° = Gibbs free energy
R = the gas constant
= 8.314 J∙mol-1∙K-1
T = temperature in Kelvin
K = °𝐶 + 273.15
Keq = equilibrium constant
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Keq =
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Ratio of conformers depends on their difference in energy

68
 Problem
What ratio of cyclohexane molecules exists in the chair versus boat
conformation at 25°C?

Half-chair Half-chair

45
kJ/mol

Boat

30

23
Chair Chair

Twist-Boat Twist-Boat

Progress 

Image and text accessed on Sept. 30, 2022: Credit:

“Cyclohexane: A Strain-free Cycloalkane”, CC BY-NC-SA’ via LibreTexts: https://chem.libretexts.org/Courses/Kenyon_College/Ch emistry_ 231_an d_232_ -_Kenyon_Colleg e_(Ge tzler_Hoff erbe rth_an d_Hunsen )/4% 3A_Cycloalkanes/4.3% 3A_Cyclohexan e% 3A_A_Strain-Fr ee_Cycloalkane
Keministi, Public domain, via Wikimedia Commons: https://commons.wikimedia.org/wiki/File:Cyclohexane_ring _flip_and_ relative_co nfor mation_e nergies.sv g 69
 Problem
Keq

Less stable boat more stable chair

𝑒𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 𝑔𝑜𝑖𝑛𝑔 𝑓𝑟𝑜𝑚 𝑏𝑜𝑎𝑡 𝑡𝑜 𝑐ℎ𝑎𝑖𝑟 𝑐𝑜𝑛𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛:

∆𝐺° = -30 kJ/mol Chair is
more
∆𝐺° = −2.303𝑅𝑇𝑙𝑜𝑔𝐾𝑒𝑞 stable than
the boat by
30000𝐽 8.314 𝐽 30 kJ/mol
− = −(2.303) (298.15 K)(𝑙𝑜𝑔𝐾𝑒𝑞 )
𝑚𝑜𝑙 𝑚𝑜𝑙 ∙𝐾

30000𝐽 5708.72 𝐽
− =− (𝑙𝑜𝑔𝐾𝑒𝑞 )
𝑚𝑜𝑙 𝑚𝑜𝑙

5.255 = log 𝐾𝑒𝑞 𝐶ℎ𝑎𝑖𝑟

Ratio = 180,000
Keq = 1.8 x 105 𝐵𝑜𝑎𝑡
Im a g e an d tex t ac ce sse d on Se pt. 3 0, 20 22 : Cred it :
70
“Cy c l o h e xan e: A Strain -free Cyc lo al ka ne ”, CC BY-NC-SA’ vi a L ib reTex ts : http s://c he m.l i brete xts.org/Co urse s/Ken yo n_ Col le ge /Che mis try _2 31 _a nd _2 32 _-_Ke ny on _Co l eg e_ (Getzl er_Hofferbe rth _a nd _Hu ns en )/4 %3 A_ Cyc lo al ka ne s/4.3%3A_ Cycl oh ex an e%3A_A_ Strain -Free_ Cycl oa l kan e
Ke m i n i s ti , Pu bl ic d om ai n, vi a Wi ki me di a Com mon s: h t ps :/ /co mmon s.wi ki med ia .org/wi ki /F i le :Cycl oh ex an e_ rin g_ fl i p_ an d_ rel ati ve_ co nforma t io n_ en erg ie s.svg
 Energy Difference and Equilibria
Less stable more stable

-G° Keq % more % less

𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 stable stable
(kJ/mol) = 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
𝒎𝒐𝒓𝒆 𝒔𝒕𝒂𝒃𝒍𝒆
=
𝒍𝒆𝒔𝒔 𝒔𝒕𝒂𝒃𝒍𝒆

0.00 1 50.0 50.0

1.72 2 66.7 33.3
3.99 5 83.3 16.7
90.9
5.71 10 = 90.9 9.1
9.1
7.42 20 95.24 4.76
17.13 1,000 99.9 0.1
22.83 10,000 99.99 0.01
28.54 100,000 99.999 0.001
* At 25°C 71
 Twist-Boat to Boat Conversion
What does a 7 kJ/mol difference in free energy look like?

Half-chair Half-chair

45
kJ/mol

Boat

30

23
Chair Chair

Twist-Boat Twist-Boat

Progress 

72
Im a g e an d tex t ac ce sse d on Se pt. 3 0, 20 22 : Cred it :
“Cy c l o h e xan e: A Stra in -fre e Cyc lo al ka ne ”, CC BY-NC-SA’ vi a L ib reTex ts : http s://c he m.l i bre te xts.org /Co urse s/Ken yo n_ Col le ge /Che mis try _2 31 _a nd _2 32 _-_Ke ny on _Co l eg e_ (Getzl er_ Hofferbe rth _a nd _Hu ns en )/4 %3 A_ Cyc lo al ka ne s/4.3% 3A_ Cycl oh ex an e% 3A_A_ Stra in -Fre e_ Cycl oa l kan e
Ke m i n i s ti , Pu bl ic d om ai n, vi a Wi ki me di a Com mon s: h t ps :/ /co mmon s.wi ki med ia .org/wi ki /F i le :Cycl oh ex an e_ rin g_ fl i p_ an d_ rel ati ve_ co nforma t io n_ en ergie s.svg
Boat vs. Twist

Boat

73
Boat vs. Twist

74
Boat vs. Twist

75
Boat vs. Twist

76
Boat vs. Twist

77
Boat vs. Twist

78
 Boat vs. Twist

Twist

Less 1-4 diaxial interaction AND less fully-eclipsed bonds 79

Boat vs. Twist

80
Boat vs. Twist

81
Boat vs. Twist

82
Boat vs. Twist

Boat

83
Boat vs. Twist

84
Boat vs. Twist

85
Boat vs. Twist

86
Boat vs. Twist

87
Boat vs. Twist

Twist

88
Boat vs. Twist

89
Boat vs. Twist

90
Boat vs. Twist

91
Boat vs. Twist

92
Boat vs. Twist

Boat

93
Monosubstituted
cyclohexanes

94
 Cyclohexane Derivatives

Replace one hydrogen atom with a methyl substituent

95
 Methylcyclohexane

One hydrogen replaced with a methyl group….are the two chair

conformations now equivalent? 96
 Methylcyclohexane
Where does the equilibrium lie….to the right or to the left?

Keq = ?

Methyl in axial position Methyl in equatorial position

97
Methylcyclohexane: Chair to Chair Flip

98
Methylcyclohexane: Chair to Chair Flip

Chair conformation I

CH3 is equatorial
99
Methylcyclohexane: Chair to Chair Flip

100
Methylcyclohexane: Chair to Chair Flip

101
Methylcyclohexane: Chair to Chair Flip

102
Methylcyclohexane: Chair to Chair Flip

103
Methylcyclohexane: Chair to Chair Flip

104
Methylcyclohexane: Chair to Chair Flip

105
Methylcyclohexane: Chair to Chair Flip

106
Methylcyclohexane: Chair to Chair Flip

Very unfavorable 1,4-diaxial interaction in the boat conformation

107
Methylcyclohexane: Chair to Chair Flip

108
Methylcyclohexane: Chair to Chair Flip

109
Methylcyclohexane: Chair to Chair Flip

110
Methylcyclohexane: Chair to Chair Flip

111
Methylcyclohexane: Chair to Chair Flip

112
Methylcyclohexane: Chair to Chair Flip

Chair conformation II
CH3 is axial
113
Methylcyclohexane: Chair to Chair Flip

Chair conformation II
• Unfavorable 1,3-diaxial interaction

114
 Methylcyclohexane

The chair conformation with the methyl group equatorial is 7.28 kJ/mol more
stable than the chair conformation with the methyl group axial.

Why?

115
 Methylcyclohexane
equatorial
Methyl group is
as far away from
the rest of the ring
as possible (anti),
 no gauche
Look this way interaction

axial Look
this way
Methyl group
is gauche to
the ring
 2 gauche
interactions
Look this way

Image adapted and text accessed on Oct. 1, 2022: Credit;

Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks: https://kpu.pressbooks.pub/organicchemistry/c hapte r/4-4 -substitu ted-cycloh exanes/
“Substituted Cycloalkanes”, CC BY-NC-SA, via LibreTexts” https://chem.libretexts.org/Bookshelves/Organic_Chemist ry/Ma p% 3A_Organic_Che mistry_(Vollha rdt_an d_Schore )/04._Cycloalka nes/4.4% 3A_Substitut ed_Cyclohexan es
116
 Methylcyclohexane
Where does the equilibrium lie….to the right or to the left?

Methyl in axial position Methyl in equatorial position

• Equilibrium lies to the right.

• The two conformers are not equal in energy.
• Equatorial methyl avoids 2 unfavorable methyl-hydrogen 1,3-diaxial
interactions.
• The 1,3-diaxial interaction is basically gauche steric strain
 Having the methyl in the equatorial position is favored by 7.28 kJ/mol

Image adapted and text accessed and slightly adapted on Oct. 1, 2022: Credit;
117
Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks: https://kpu.pressbooks.pub/organicchemistry/c hapte r/4-4 -substitu ted-cycloh exanes/
“Substituted Cycloalkanes”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Bookshelves/Organic_Che mistry/M ap% 3A_Organic_Che mistry_ (Vollhardt_a nd_Schore )/04. _Cycloalkanes/4. 4% 3A_Substituted_Cyclohexa nes
 Methylcyclohexane
Calculate the percentage methylcyclohexane that exists in the equatorial
conformer compared to the axial conformer at 25°C?

Given: The equatorial conformer is favored by 7.28 kJ/mol

Text accessed and slightly adapted on Oct. 1, 2022: Credit;

118
Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks: https://kpu.pressbooks.pub/organicchemistry/c hapte r/4-4 -substitu ted-cycloh exanes/
“Substituted Cycloalkanes”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Bookshelves/Organic_Che mistry/M ap% 3A_Organic_Che mistry_ (Vollhardt_a nd_Schore )/04. _Cycloalkanes/4. 4% 3A_Substituted_Cyclohexa nes
 Methylcyclohexane
∆𝐺° = −2.303𝑅𝑇𝑙𝑜𝑔𝐾𝑒𝑞
7280 𝐽 8.314 𝐽
− = −(2.303) (298.15 K)(𝑙𝑜𝑔𝐾𝑒𝑞)
𝑚𝑜𝑙 𝑚𝑜𝑙 ∙𝐾
7280 𝐽 5708.72 𝐽
− =− (𝑙𝑜𝑔𝐾𝑒𝑞)
𝑚𝑜𝑙 𝑚𝑜𝑙
1.2752 = log 𝐾𝑒𝑞
Keq = 18.85

Let x = axial methyl conformer

Let y = equatorial methyl conformer

Know:
x + y = 100% Two equations, two unknowns
𝑦
= 18.85
𝑥
Thus substitute 18.85x = y into first equation
x + 18.85x = 100%
19.85x = 100%
x= 5.0%
95.0% of the time the methyl group is in the equatorial positon and 5.0% of
the time it exists in the axial position.
119
 Energy Difference and Equilibria
Less stable more stable

-G° Keq % more % less

𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 stable stable
(kJ/mol) = 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
𝒎𝒐𝒓𝒆 𝒔𝒕𝒂𝒃𝒍𝒆
=
𝒍𝒆𝒔𝒔 𝒔𝒕𝒂𝒃𝒍𝒆

0.00 1 50.0 50.0

1.72 2 66.7 33.3
3.99 5 83.3 16.7
90.9
5.71 10 = 90.9 9.1
9.1
 the values for
7.42 20 95.24 4.76 methylcyclohexane
17.13 1,000 99.9 0.1
22.83 10,000 99.99 0.01
28.54 100,000 99.999 0.001
* At 25°C 120
 Energy cost having an axial substituent in a
monosubstituted cyclohexane
Substituent -G° (change from axial to 𝒆𝒒𝒖𝒂𝒕𝒐𝒓𝒊𝒂𝒍
Keq =
R equatorial orientation) kJ/mol 𝒂𝒙𝒊𝒂𝒍

(Energy cost of having substituent

axial – steric strain due to 1,3- diaxial
interactions)
methyl 7.28 18.8
ethyl 7.49 20.5
isopropyl 10.92 81.8
tert-butyl 23.01 10732
chloro 1.67 2.0
• the bigger the substituent the more favored is the chair form with the
substituent in the equatorial position
 Less repulsive interactions!

121
Te x t a c ces se d on Oc t. 1, 20 22 : Cre di t:
“Su b s ti tuted Cy cl oh ex an es”, CCBY-NC-SA, vi a Li bre Te xts: h t p s:// ch em.l ib retex ts .o rg/Boo ksh el ve s/Orga ni c_ Che mi stry /M ap %3A_ Orga ni c_ Che mis try _(Vol l ha rd t_a nd _Sch ore )/0 4._Cy cl oa lk an es/4 .4 %3 A_ Sub stit u te d_ Cycl o he xan es
Co n fo rm a ti on s of Dis ub stit u te d Cyc lo he xa ne s”, CC BY-NC-SA, vi a L ib reTex ts : https://c he m.li brete xts.org/Bo ok she l ves /Organ ic _Ch emi stry/Orga ni c_ Che mi stry _(Lib reTex ts )/0 4%3 A_Organ ic _Co mpo un ds -_ Cyc lo al ka ne s_ an d_ th ei r_Stereoch em is try/4 .0 8%3A_Co nfo rm atio ns _o f_ Di sub sti tu te d_ Cyc lo he xa ne s
 t-butylcyclohexane

Keq = 10732

t-butyl group in axial position t-butyl group in equatorial position

 A tert-butyl group is so bulky, that the equatorial position is

overwhelmingly favored over the other chair conformation
where it would be in the axial position
• About 99.99% exists in equatorial, 0.01% in axial

122
 1,2-Disubstituted cyclohexanes

• Larger groups produce more steric strain when they occupy axial
positions.
• If one of the two groups must be in the axial position, a more stable
conformation would be generated when the smaller substituent is in
the axial position. This avoids greater steric strain due to 1,3-diaxial
interactions.
• The energy cost of having an axial isopropyl group is 10.92 kJ/mol,
whereas it is 7.28 kJ/mol for the methyl group
 The more stable cis-1-isopropyl-2-methylcyclohexane
conformation has an equatorial isopropyl group
Text accessed on Oct. 1, 2022: Credit;
Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks : https://kpu.pressbooks.pub/organicchemistry/chapter/4 -4-substituted-cyclohexanes//
123
“Conformations of Disubstituted Cyclohexanes”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_(LibreTexts)/04%3 A_Organic_Compounds -_Cycloalkanes_and_their_Stereochemistry/4 .08%3 A_Conforma tions_of_Disubsti tuted_Cyclohexanes
 Convert planar structure to chair
cis-1,2-dimethyl cyclohexane

up, up
2 substituents up
• It doesn’t matter where you begin or if
you begin with equatorial or axial.
• The important thing is whether the
groups are pointing UP or DOWN
• Just maintain the same order of
substituents and direction when
numbering the chair
124
 In Class Problem

True or false: The molecule is cis-1,2-dimethylcyclohexane.

True or false: A ring flip of the above structure generates the one below.

125
Images accessed, text adapted and accessed on Dec. 10, 2022: Credit: Xin Liu, Organic Chemistry I, CC BY-NC-SA 4.0, via Pressbooks : https://kpu.pressbooks.pub/organicchemistry/chapter/4 -4-substituted-cyclohexanes/
Relative stability of cis and trans isomers
of disubstituted cyclohexanes –
considering conformations

126
Convert planar structure to chair: Relative stability of
conformers
cis-1,2-dimethylcycohexane

Keq = 1

• Both methyl • Both methyl groups pointing up

groups are • Both conformers equally stable since both have 1
pointing up axial, 1 equatorial substituent

trans-1,2-dimethylcycohexane

Lower energy conformation

• One methyl group pointing up, one pointing down.

• 1 methyl
• Diaxial conformers is 14.56 kJ/mol (2 x 7.28 kJ/mol) less
group point
stable due to 1,3-diaxial interactions than the diequatorial
up, 1 down
conformer
• Equilibrium favors the diequatorial conformer
127
Images and text accessed slightly adapted on Oct. 2, 2022: “Conformations of Disubstituted Cyclohexanes” CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Courses/Siena_Heights_Unive rsity/SHU_Organic_Ch emistry_ I/3% 3A_Chapter _3_Confo rmatio ns_and_Cycl oalka nes/3.0 9% 3A_Conforma tions_of_Disubs tituted_Cycloh exanes
Convert planar structure to chair: Relative stability of
conformers
cis-1,3-dimethylcycohexane

Lower energy conformation

• Both methyl groups pointing down
• Both methyl • Diaxial conformers is 14.56 kJ/mol (2 x 7.28
groups are kJ/mol) less stable than the diequatorial conformer
pointing down due to 1,3-diaxial interactions
• Equilibrium favors the diequatorial conformer

trans-1,3-dimethylcycohexane
Keq = 1

• 1 methyl • One methyl group pointing up, one pointing down.

group point • Both conformers equally stable since both have 1 axial, 1
up, 1 down equatorial substituent
128
Images and text accessed on Oct. 2, 2022: “Conformations of Disubstituted Cyclohexanes” CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Courses/Siena_Heigh ts_University/SHU_Org anic_Chemist ry_I/3% 3A_Chapte r_3_Con form ations_an d_Cycl oalkanes/3 .09% 3A_Confor mations_o f_Disubstitute d_Cyclohexanes
 Problem
Draw chair forms of cis and trans-1,4-dimethylcyclohexane and predict
which geometric isomer is the most stable.
cis-1,4-dimethylcycohexane

trans-1,4-dimethylcycohexane

Lower energy conformation

• With the cis isomer, both conformations have 1 axial and 1 equatorial methyl group.
With the trans isomer, a diequatorial conformation exists.
• Equatorial position avoids 1,3-diaxial interactions.
 The trans isomer is more stable than the cis.

always think whether you can draw a more stable chair form!
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Problem and text accessed on Oct. 2, 2022: Credit: Melanie Cooper and Michael Klymkowsky, OCLUE: Organic Chemistry, Life, the Universe & Everything, CC BY-NC-SA 4.0, https://openbooks.lib.msu.edu/oclue/chapter /chapte r-3 -confo rmations -and -configu rations- the-co nsequenc es-of -the- three -dimensio nal-nat ure- of-ca rbon-c ompou nds/
 In class problem

Is the following statement True or False? If False, briefly explain

why.

During a cyclohexane ring flip, a cis isomer is converted to a trans

130
Problem taken on Oct. 1, 2022: Credit; Tim Soderberg, “Conformations of cyclic organic molecules”, CC BY-NC-SA, via LibreTexts : https://chem.libretexts.org/Under_Construction/Purga tory/Book %3A_Organic_Chemis try_with_a_Biolog ical_Emphasis_(Soderberg)/Chap ter_03%3 A_Conforma tions_and_S tereochemistry/03.2 %3 A_Conforma tions_of_cyclic_organic_molecules
Problem: Disubstituted cyclohexanes with 2 different substituents
(a) Draw the most stable chair conformation of (1S,3S)-1-chloro-3-
methylcyclohexane
(b) How much more stable (in kJ/mol) is that conformer?
Strategy:
1. Draw bond line structure for cyclohexane
2. Place substituents around the ring
3. Orient the bonds based on absolute configuration S S
4. Convert bond-line structure to chair form
5. Draw conformers

More stable conformer

An axial methyl group destabilizes the conformer by 7.28 kJ/mol due to 1,3-diaxial
interactions, whereas an axial chloro groups destabilizes the conformer by 1.67
kJ/mol. Thus, the axial chloro conformation is lower is energy and thus more stable.
The axial chloro conformer is more stable by:
G° = ∆𝐺 ° 𝑚𝑒𝑡ℎ𝑦𝑙 𝑔𝑟𝑜𝑢𝑝 𝑎𝑥𝑖𝑎𝑙 − ∆𝐺 ° 𝑐ℎ𝑙𝑜𝑟𝑜 𝑔𝑟𝑜𝑢𝑝 𝑎𝑥𝑖𝑎𝑙
G° = 7.28 kJ/mol – 1.67 kJ/mol
G° = 5.61 kJ/mol
Problem adapted on Oct. 3, 2022: Credit: Conformations of Disubstituted Cyclohexanes”, CC BY -NC-SA, via LibreTexts: https://chem.libretexts.org/Courses/Brevard _College/CHE_201% 3A_Organic_Ch emistry_ I/02% 3A_Alkanes_and_Cycloalka nes/2.1 6% 3A_C onforma tions_of_Disubs tituted_Cycloh exanes 131
 Planar vs conformational representations

Planar Representation Conformational Representation

1,3-diaxial interactions 23.01 kJ/mol

Keq 569

1,3-diaxial interactions 7.28 kJ/mol

More stable conformation

• Since there is an equilibrium between conformers, it is better to show

conformers rather than planar representations.
• Compounds will spend the majority of the time in the more stable conformation. 132
Pro b l e m an d te xt acc es sed an d ad ap te d o n Oct. 3 , 20 22 : Cred it : Co nforma ti o ns o f Di sub sti tu te d Cyc lo he xa ne s”, CC BY -NC-SA, v ia L ib reTex ts : https :/ /che m.li b re texts.o rg /Cou rs es /Brev ard _Co l eg e/CHE_2 01 %3 A_Orga ni c_ Che mi stry_I/02 %3 A_ Alk an es _a nd _Cyc lo al ka ne s/2.1 6%3 A_Co nforma tio ns _o f_ Dis ub stit u te d_ Cycl o he xan es
Fused & Bridged Bicycloalkane: IUPAC Nomenclature

• A bridged bicycloalkane has • A fused bicycloalkane has

two adjacent rings but the two two adjacent rings and the
bridgehead carbons are two bridgehead carbons are
separated by at least 1 carbon adjacent to each other

Bridgehead
carbons

Bridgehead
carbons

bicyclo[2.2.1]heptane bicyclo[2.1.0] pentane

FOR THIS COURSE: DO NOT WORRY ABOUT NAMING

BICYCLOALKANES WITH SUBSTITUENTS
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Te x t a d ap te d sl i gh tl y wi th pe rm is si on o n Dec . 2 9, 2 02 2: Cre di t: Ja mes As he nh urst, “Nam in g Bicy clic Compounds – Fuse d, Bridged, a nd Spiro”, vi a Ma steri ng Org an ic Ch em is try: h ttp s:// www.mas te rorg an ic che mi stry.com /2 01 4/08 /14 /b rid ge d-b ic ycl i c-co mpo un ds -a nd -ho w-to -na me-the m/
Fused & Bridged Bicycloalkanes: Nomenclature
1. Name the parent alkane as the number of carbons total in all the rings.
6
5 1
7 7 carbons, thus heptane
4 2
3
2. Number from a bridgehead, along longest bridge back to the bridgehead,
then along the next longest bridge, etc.
1 1
1
2 2

3. Add ‘bicylo’ in front of the name of the parent chain followed by [ ]

brackets. Show the lengths of bridges (number of carbons) in the
brackets, from longest to shortest.
1 1
1 1 2
1 2
2 2 3
4 3
Bicyclo[2.2.1]heptane Bicyclo[4.3.0]nonane 134
 Problem
a) Draw cis-bicyclo[3.3.0]octane

b) Draw cis and trans-bicyclo[4.4.0]decane (ALSO CALLED DECALIN)

cis trans

 

• These are diastereomers, they are not mirror images of each other
• In terms of sterics, more steric interactions with cis-decalin since one carbon of the second
ring can be considered to be an axial substituent of the first ring, whereas both carbons are
considered to be in an equatorial position with respect to the first ring in trans-decalin
• cis less stable than trans since cis has two 1,3-diaxial gauche interactions and the trans has
none
Im a g e s o btai n ed a nd te xt a da pted sl ig htl y wit h p ermi ssi o n on De c. 29 , 20 22 : Cred it : J ame s Ash en hu rs t, “ Fuse d Rings – Cis-De ca li n a nd Trans-De ca li n”, v ia M aste rin g Orga ni c Che mi stry : https://www.ma stero rg an i cch emi stry.co m/20 14 /0 8/05 /fu se d-rin gs /
135