R.
For example
A 4
oN ACH Note: In this case 4th group is above the plane
"
Br’
1
Case IMI: Ifthe fourth group is on the
group undergoes below the plane.
sPr__S0, clockwise movement gives'S"
3
plane then do double interchange in such a way that the 4th
For example:
4
H
1 Coney 2
HO~ Q/CH,CH; In this case 4th group is on the plane.
CH;
3
2
i fim a
Con, Ist Cosy 2nd Cig
Ho WCC a HO Neg, ee SCT SE
i
R/S Nomenclature in Fischer projection.
Horizontal Line
co. Interaction of these two lines represent C-atom
Vertical Line
Vertical line + away from the viewer.
Horizontal Line -> Towards the viewer.
108 | Stereochemistry , @)
CHEM ACADEMY
‘Towards the viewer
away from the viewer
=> Assign priority sequence,
Case I: If 4th group is present on the top or bottom of vertical line then
HP. Lip, > Clockwise > R
LP. HP. > Anticlockwise > S
For example:
4
1
H NH.
2 WG, »
H3C COOH FatD-coon
3
NH, S HC HOR
1 4
‘Case II: If 4th group is present on left or right side of the horizontal line then.
ah f
L, HP.
Anticlockwise moment > R
Clockwise ~» Movement -> S
For example
3
CH
NH)
COOH
Rag
For example
CONVERSION OF FISCHER -> WEDGE
CH HC. ci
con ™,
h H “oH
Stereochemistry | 109 UFJAM/M.Sc. Entrance
CH,0H HOH,C. OH —_HOH,C. ,OH
HO-—H Ga 4
H-—0H JH or Hy,
Et Et OH HO Et
CH; HyC,0H = HC,0H HY cH,
HO-}-H iy 7 HON
H-cH, == WH or or AH
OH HO “CH, H3C’P OH Ho’ “CH,
Note: In all conversion,
CH;
H—-—OH
H-—0n ==
GHs
CONVERSION OF FISCHER TO
CH
“on
Ho
CHS “OH
Hy
r
©
the configuration (R/S) should not be change.
HAC,
BC. ,H
T#
HOTS GH,
SAWHORSE,
Fow
be aim carbon
H ‘OH
H>J-OH
J Css
First carbon
HoH
At first carbon Y
C,H;
and then combine these two by a strai
CH;
H--on Hn onfVOH
H-y-0H __, cH
GH CiHs .
Note: Since Fischer projectiomis repr
Note: Consi
Y (Pronow
also be in eclipsed form if we have need of staggere:
110 | Stereochemistry
jider at first carbon shape like
inced ‘Y”)
H
At 2nd carbon Y
cH,
OH
ight line like
Ph
Me——H
Me——H ——>
OTs
resented in eclig
Me, ye
Ph
OTs
ipsed form so the resulting sawhorse should
'd form we can obtain it by simply rotation ©
CHEM ACADEMY
For example:
Me,
Me, Met
Ph Me Ph
OTs ots
i Staggered form and this form is suitable for eimination reaction
eclipsed form
since for E, elimination, the two departing group should be trans.
(Sen,
Mé Ph HO OPh
+ C\H,OH + OTs
CONVERSION OF FISCHER TO NEWMANN
cH, c
yg tateabon of tn,
HOT GHs Bo. Hs
Homi = Smee} ot
tee e cw =
peed form Te L
Hs
gon 4 on
oH
de OH CH,OH
eames
Coon. Prd carbon cy '0OH
Ho. H
nt ow
HoH
7, won Ho’ "
1st carbon 2nd carbon soon st carbon coon
coon
How we can apply these interconversion into react
Let us consider addition of Br, on cis-2-butene.
Hs
ney + Br
H
yn mechanism.
Stereochemistry | 111 FJAM/M.Sc. Entrance
Ce 2 oom poe
a %, " 4
mM NEY, |
nee. a 0 al we 8 Simply ey oH
te rotation
4
Msc a
ow a A aft Ve
lie 8 ction
oo, ,— b= ts
H Be ad H CHa cx, ®)
So, A and B are non super impossable mirror image to each other and hence it isan enantiomer.
”
CONVERSION OF NEWMANN INTO FISCHER AND RELATION BETWEEN TWO
COMPouNDs.
H rl
a Br H Cols
Cy ‘OH HC Br
chy on
w ©
[ I
Ls as} cl. ‘Br ‘Since, in (B) C,H, gr, is attached
cr Ho: with back carbon and we want to
bring it at font carbon so we
CH; CoH; willhave to rotate itby 180”
GHy cH
(A) 6)
1
H 1H
Br _
cH,
He ®
So, A and B are diastereomers.
Br
Bi
H Ph art
Ph
HC NIz @& HC NH),
cl H
(A) (®)
What is the relation between A and B.
112 | Stereochemistry ®)
0)
CHEM ACADEMY
cl H
Br NH) Br. NH,
H cl
Ph
CH3 ue CH;
Ph Ph
cit H-F Cl
Brs[aNh Br—-NHy,
CH; CH;
it see Tener,
So, these two are diastereomers
ENANTIOMERS
Enantiomers are the stereoisomers which are nonsuper-imposable mirror images to each other.
So these two stereoisomers have opposite descriptor.
HjCS4H {| Ha CH.
oe “on H Ho SCH,
s ‘ R
+ Non super imposable mirror image.
+ Opposite descriptor i.e. one is R and other is S.
, tb CH,
nia ci +H
HW SH
GHs CoH
(A) (B)
So, in compound ‘A’ and ‘B’, the configuration at chiral centre are
InA InB
G—S ©G—R
G—R GS
Properties of enantiomer:
| So, these two are enantiomer
1. Allphysical properties such as M.P,, refractive index, vapour pressure, relative density, NMR
spectrum, IR spectrum are same except direction of optical rotation. (Magnitude is same but
direction is opposite).
2. Allthe chemical properties of enantiomers towards achirat reagent are always identical.
3. The chemical properties of enantiomers will be same in the achiral medium.
DIASTEREOISOMERS
Diastereomers are the stereoisomers that are not mirror image of each other.
Stereochemistry | 113 )
:
‘
:
.
NTJAM/ M.Sc. Entrance
‘Some Important Points Regarding the Diastereoisomers
1. Diastereomers can arise when structures have more than one stereogenic centre.
2 The magnitude of optical rotation of diastereoisomers are always different but the direction
may be same or opposite.
3. The physical properties of diastereomers are always different but difference may be more or
less,
4. The chemical properties of diastereomers toward chiral as well as achiral reagent is always
different.
Examples of diastereoisomers:
HO,
COH HOC CoH
Fumarie acid Maleic acid
mp. 299-300°C mop. 140-142°C
Bcometrical isomers (ie. cis and trans Isomers) are always diastereoisomers.
A similar stéFeoisomers can exist in cyclic compounds.
For example: 4-1-butyl cyclohexanol,
\OH H
“H Con
cis-isomer ‘Trans-isomer
because ~OH and t-Bu group m.p. 80-81°C
are projected in same direction
m.p. 82-83°C_
So, these two stereoisomers are called diastereomers,
Note: Diastereolsomers can be chiral or achiral,
7 ig
ee
So, achiral-diasteromers.
Ara _sCOMe Ara gcomMe
Ow ow
These two diasteroisomers are chiral because
plane of symmetry or COS are not present.
* on These two are
ephedrine Pseudoephedrine
114 | Stereochemistry (10)
qa
CHEM ACADEMY
Remark:
The diastereoisomers are different compounds with different names (For example ephedrine and
Pseudoephedrine) and different properties, while the pair of enantiomers are the same compound and
differ only in the direction in which they rotate polarize light.
In summary if we have compound having two chiral centre each one R/S then
ener
= =e
For example:
pH OH
= 9
feos :
“4 coo
— tow
F
Q oe
HLS ge econ
x "3
MESO COMPOUNDS
Compounds that contain sterogenic centres but are themselves achiral are called meso compounds.
‘This means that there is a plane of symmetry or centre of symmetry with R stereochemistry on
one side and ‘S’ stereochemistry on the other.
For example:
Plane of symmetry
‘optically inactive Plane of symmetry
Hooc, | cou
nd J “ow
on
‘Mirror’plane ‘So Meso Compound Plane ofsymmety Br
Optically inactive —rAchiat ‘Meso Compound
SMesceompound
RELATIVE CONFIGURATION (D- AND L-NOMENCLATURE)
‘The term relative configuration is used when a molecule is assigned configuration with respect
to glyceraldehyde. In glyceraldehyde if-OH group is present on the right hand side, itis assigned
D-configuration and if -OH group is on the left hand side, it is assigned L-configuration but
most oxidised group should be on top.
Stereochemistry | 115 NT-JAM/M.Sc. Entrance
The-OH
The ~OH oniet
0 group
oO & right gHo gue
H—-—on HO™C=H = HO——H
CH,OH CH,OH CH,OH CH,OH
D-Glyceraldehyde L-Glycerafdehyde
Compounds prepared from or converted into D-glyceraldehydes belong to D-series. Similarly
Sompounds prepared from or converted into L-glyceraldehydes belong to the L-series.
am The D- and L-
Nomenclature is independent of dextro- and laevo-
. Acompound of D-series may
L-series compounds may show (+) or (—) optical
differ in the stereochemistry at only one sterocentre.
to the chiral compound having more than two chiral center,
be dextro (+) or leavo (-) rotatory. Similarly,
activity.
* This nomenclature system is used in carbohydrates and amino acids
(2) EPIMERS
Epimers are the diasteromers,
The term can be applied only
For example glucose and glactose are epimers at C,
1 CHO CHO
CH,0H
Glucose Galactose
Similarly glucose and mannose are epimer at C,
1 CHO
R 4H——OH
R sH--oH
6CH,OH CH,OH
Glucose Mannose
0 +
(A) ®) on
Compound (A) and (B) are epimerie pair,
(13) ANOMERS
Anomers are the diasteromer (in the case of monosaccharide
Cl are the called anomers.
116 | Stereochemistry
) which differ in the configuration at CHEM ACADEMY
20H
Ys On ey on omeme
HH
o OH KG WA
H OH
o-anomer H OH
a-D-glucose B-D-glucose
(14) THREO AND ERYTHRO NOMENCLATURE
Threo and Erythro nomenclature are based on sugar chemistry.
CHO CHO
H ‘OH HO—-H
H--0H H—-O0H
CH,OH CH,OH
DOerythrose DO)threose
cS Erythrose and threose are diasteromers.
. A molecule with two adjacent stereocentres, when there are two. groups which are common to
each carbon while third is different i.e. C,,, ~C,, gives rise to erythrose and threo diastereomer.
Procedure for finding erythrose and threose diastereomers.
Step I: Find out the group or atom which is not common on two adjacent asymmetric centre.
Step II: Placed this different group on top and bottom position of vertical line in Fischer projection
formula.
Step III: And arrange the rest group or atoms around horizontal position of Fischer projection.
Step IV:
Case I: If two similar group are on the same side then it is called erythrose.
Case II: If two similar group on the opposite side then it is called threo.
For example:
These two are different group on the two
— asymmetric carbon placed at top and bottom.
CHy
“These two H, atoms are projected in similar side so it erythrose
CH,CH;
bed Inthis structure the two similar group viz H and Br are opposite so, itis threo.
CH,
Note: The terms erythro and threo are generally applied only on those motecules which do not
have symmetric ends.
Stereochemistry | 117 NTJAM/M.Sc, Entrance
as)
In summary, condition for erythro and threo nomenclature:
(1) Two asymmetric carbon should be there
@) On two asymmetric carbon, two of the groups are the same and the third is diferent.
GEOMETICAL ISOMERISM
The compounds having similar molecular formulae but different arrangement of atoms or groups
in space around the double bond are called geometrical isomers and the phenomenon is known
&5 geometrical isomerism, The geometrical isomerism arises due to restricted rotation about a
carbon-carbon double bond, A complete rotation around carbon-carbon double bond causes the
breaking of x bond.
Necessary and sufficient condition for geometrical isomerism
An alkene of the type abC = Cxy exhibits geometrical isomerism if a b and x # y. In an alkene,
ifeither ofthe double bonded carbonsis attached to two identical groups or atoms, no geometrical
isomerism will exist,
eae [oes
~ fas band rey,
b Ny
Ae Cty
Nn Hn” Nu, cH” SCH
eee
There are three different ways in which groups a, b, x and y can be arranged around carbon-
carbon double bond. The configuration of the geometrical isomers is designated by
+ Cis-trans system + E-Zsystem
Cis-trans system: This system is used for designating the alkenes in which the two olefinic
carbons have at least one similar group or atom present on them. For example, the alkenes ofthe
type abC=Cab and abC = Cax exhibit cis-trans isomerism. Tt is to be noted that
(i) the term cis- is used when two similar atoms or groups are present on ‘same sides across the
double bond and
(ii) the term trans- is used when two similar atoms or ‘groups are present on Opposite sides across
the double bond.
oy
8s,
Joh yy ci
Nu Hn” ‘coon Hn “a
‘The cis- and trans- isomers differ in their physical properties. In general, trans- isomers are more
stable compared to cis- isomers. In cis-isomers, the groups present on the same side experience
van der Waals repulsive forces due to steric factors.
CH,
118 | Stereochemistry i
CHEM ACADEMY
‘rans. More abe dee Les nable
Dipole moment values can be used effectively for distinguishing cis- and trans-isomers. The
rans-isomers have zero dipole moment as the bond dipole on opposite sides cancel each other.
cg oe
i ti
7a Nn
uso
E-Z system
The alkenes of the type abC = Cxy exhibit geometrical isomerism but they cannnot be classified
as cis- or trans- isomers, as all the substituents attached to olefinic carbons are different. The
configuration about any carbon-carbon double bond is specified using E-Z system. The sequence
rules as discussed earlier are used for this purpose.
The atoms or groups attached to each olefinic carbon are given priority as per sequence rules
described earlier.
Ifhigher priority groups are present on same sides across the double bond, the geometrical isomer
is said to have Z-configuration.
‘or Sige oe Hite
te ae
8 Br He Bi ‘Toe pricy of
, a, Poem
o=c’, ae oe
rac a” Non accordance with
eee
vier F "Sone wwe F Soe
mes vy ly “ay
B z
tiger tower tate
iy os
we 1 a 1
HoocL Hl HNL Br
cacy 7 ce,
ng” Sd a Noa
uw Ste tae SS te
Ea = tS os
z z
erp goer to eee
ee rae, ca ate tae
If higher priority groups are present on opposite sides across the double bond, the geometrical
isomer is said to have E-configuration.
All geometrical isomers (including cis- and trans-) are designated by E-Z system.
Stereochemistry | 119 NFJAM/M Sc. Entrance
2
H.
1
CH. Yc I, COOH
c= =C_
Hv ON Hooc~ (NH
7 2 T 2
eae (©)B1t2-enedioe acid
cis- But-2-ene 7
a Q cis-trans and E-Z
“H; CH, nomenclature are
Noeo’ independent of each
other
a” Na ‘Reis isomer cn be
2 a Eorz Similarly,
©2Chorobur2-ne (2)2-chtorobue-2ene 8 trans isomer can be
o fe iBsigned E orZ
is: 2-Crorobut2-ene ‘ran 2-Chlorbut2-ene somencloture
. _. NoacZ la:
* Geometrical isomerism is not restricted to carbon-carbon double bond [ Pee << but is
also exhibited by compounds having a carbon-nitrogen double bond [ec =N | as in oximes,
OF nitrogen-nitrogen double bond [—N = NJ as in azo compound.
According to the sequence rules a lone pair gets the least priority and is ranked below hydrogen.
Tet us consider the isomeric oximes and azo compounds and designated them as E-Z isomers
Hey
CoN
‘oH
ods
‘N
ao engoed
Leeper
ss pore iow pegs
LW 1 1 2
Hen CH es He,
= Ne ‘c:
oN 3 Z
y HG
6 @ rey
Calculation of Stereoisomer
Im order to calculate total stereoisomer, first of all we will find the value of n’
Here
n= number of site threw which stereoisomerism is observed,
Case - 1: Compound having unsymmetrical terminals or compound is unsymmetrical then total
stereoisomers is equal to 2".
CH; ~ CHOH-CHOH-C,H.
Stereoisomer = 2? = 4
Racemic pair = Enantiomerie pair = = =2
‘Meso compound (optically inactive) = 0
Case - 2: Symmetrical compound
120 | Stereochemistry @ n=even
CH; -CHOH-CHOH-cH,
Stereoisomer
ay Bt
Optically active = 2”-'
Optically inactive / Meso = ,(°-")
AG
Optically active
Racemic pair = a
(ii) n = odd
(CH, -CHOH -CHOH -CHOH-CH;
Stereoisomer = 2"
1
a
Stereoisomer = (
optically active
Optically a
2
SPECIFIC ROTATION
Racemic pair =
(16)
I
ae
(CHEM ACADEMY
Specific rotation as optical rotation of | gm/mL concentrated solution when path length 10 em(1
dm) at particular wavelength (2) of light.
fa=5
o> is a additive property
[a] is not a additive property.
Note: Most [i] values are quoted as fo], (where the D indicates the wavelength of 589 nm, the
D line of a sodium lamp) or (cry, the 20 indicating 20°C.
‘Mustration:
20 mg mandelic acid was dissolved in 1 cm of ethanol and the solution placed in a 10cm
Jong polarimeter cell. An optical rotation a: of—4.35°C was measured (that is, 4.35° to the
left) at 20°C with light of ‘wavelength 589 nm. What is the specific rotation of the acid?
a
lolp
ex!
Since, a =—4.35°
¢ =28 mg/cm?
c= 28 x 10° g/cem*
¢ = 0.028 g/cm?
Solution:
a _ -435
cx! 0.028x1
So, [als =
=-155.4
1=10cm=1 dm
Stereochemistry | 121 MT-JAM/MSc. Entrance
So, the specific rotation of mandelic acid = -155.4°.
(17) ENANTIOMERIC EXCESS
Enantiomeric excess or ¢ e is a measure for how much f one enantiomer is present compared to
the other. —_—_
For example, in a sample with 40% ¢ in R, the remaining 60% is racemic with 30% of R and
30% of S so that the total amount of R is 40% + 30% = 70%.
fo.
% optically purity = jel «100
nas
assuming a linear relationship between [i] and concentration, which is true for most cases. The
optical purity is equal to percent excess of one enantiomer over the other
So,
RI-[S 9
Optical purity = percent enantiomeric excess = a a *100 = %R—4S
lOptical rotation = Tog specific rotation|
Mlustration: Calculate the optical rotation from the given data
sp = 20°
= 90%
1=10%
€ © = 90% 10%
ee = 80%
80
je ion = ——x20=16
So, Optical rotation = 75
¢ — Optical rotation
specific rotation
100]
Mlustration: Calculate enantiomeric excess from the given data
sp rotation = 20°
optical rotation = 18°
18
jon: €& =——x100
‘Solution: 7)
ee=90%
J Since, % ofd +%1= 100
% of d~-% 9M=ec¢
So, % of 2d = 190
190
- of d= - = 95% & %1=5%
122 | Stereochemistry ‘CHEMACADEMY
(18) STEREOCHEMISTRY OF BIPHENYL, SPIRANES, ALLENES AND ALKYLIDENE
@
Gi)
CYCLOALKANES.
Biphenyls containing four large groups in the ortho positions cannot freely rotate about the central
bond because of steric hindrance. In such compounds, the two rings are in perpendicular planes.
If either ring is symmetrically substituted, the molecule has a plane of symmetry. For example,
consider the biaryls:
cl,
No: ' On, o|
o HOOC, Ss ' COOH %
HOOC’ ‘COOH |
LN ON
Ring B is symmetrically substituted. A plane drawn perpendicular to ring B contains all the
atoms and groups in ring A; hence, it isa plane of symmetry and the compound is achiral. On the
other hand, consider:
coon ON
HOOC
Mirror
There is no plane of symmetry and the molecule is chiral; many such compounds have been
resolved. Note that groups in the para position cannot cause lack of symmetry. Isomers that can
be separated only because rotation about single bonds is prevented or greatly slowed are called
atropisomers.
In allenes, the central carbon is sp bonded. The remaining two p orbitals are perpendicular to
cach other and each overlaps with the p orbital of one adjacent carbon atom, forcing the two
Femaining bonds of each carbon into perpendicular planes. Thus allenes fall into the category
represented by (4).
nee a 1 A
a” iy 3
Mirror
@)
Like biphenyls, allenes are chiral only if both sides are unsymmetrically substituted. For example,
Hone. a
H
FECT nactive Inactive Active >
So
These cases are completely different from the cis—trans isomerism of compounds with one double
bond. In the latter cases, the four groups are all in one plane, the isomers are not enantiomers, and
neither is chiral, while in allenes the groups are in two perpendicular planes and the isomers are
Stereochemistry | 123 UT-JAM/M.Sc, Entrance
@ pair of optically active enantiomers. . ;
When three, five, or any odd number of cumulative double bonds exist, Cheha ae
the four groups to occupy one plane and cis-trans isomerism is observed. y F seep rany
even number of cumulative double bonds exist, the situation is analogous to S
and optical activity is possible. ; 7
Gi) Among other types of compounds that contain the system illustrated in (6a) as that are similarly
chiral if hoth sides are diasymmetric are spiranes (e.g., (6b)) and compounds wit cyclic
double bonds (¢.g., (6c)). Atropisomerism exists in (1,5)-bridgedcalix[8]arenes.
MexC Mey re NH: F H
(c=c=c=c=c _ ,, ¢
mi 5 c
FQ OK,
a a
6(a) 6(b) 6(c)
(iv) R/S Nomenclature:
Note: Near groups be given priority over the far groups.
Alllenes
A
Cols CoH eye oHs
CN + > cat CoHs
Cot, Cot ye Ge aR
3
3
Me Ht eye
Ye
H Me 1
7 Br
eye J
s,— re, >
I
Alkylidenecyclo alkane
00) 3
viev KO - Pie
os —_—
view Mé H H ot
124 | Stereochemistry as)
CHEM ACADEMY
'S03H
CONFORMATIONS OF ALKANES : ROTATION ABOUT CARBON-CARBON BONDS
The different spatial arrangements of the atoms that result from rotation about a single bond are
called conformations. A specific conformation is called a conformation isomer or a conformer.
When rotation occurs about the carbon-carbon bond of ethane, two extreme conformations can
result—a staggered conformation and an eclipsed conformation. An infinite number of
conformation between these two extremes is also possible.
Compounds are three dimensional, but we are limited to a two-dimensional sheet of paper when
we show their structures. Perspective formulas, sawhorse projections, and Newman projections
are methods chemists commonly use to represent on paper the three-dimensional spatial
arrangements of the atoms that result from rotation about a o bond. In a perspective formula,
solid lines are used for bonds that li in the plane of the paper, solid wedges for bonds protruding
Cut from the plane of the paper, and hatched wedges for bonds extending behind the paper. In a
sawhorse projectioin, you are looking at the carbon-carbon bond from an oblique angle. In a
Newman projection, you are looking down the length ofa particular carbon-carbon bond. The
carbon in front is represented by the point at which three bonds intersect, and the carbon in back
is represented by acircle. The three lines emanating from each ofthe carbons represent its other
formations ofalkanes, we will use Newman projections because
three bonds. In discussing the co :
they are easy to draw and they do a good job of representing the spatial retationships of the
substituents on the two carbon atoms.
Stereochemistry | 125. NT-JAM/M.Sc. Entrance
gered conformation for ‘eclipsed conformation for
routon about the carbon-carbon rotation about the carbon-carbon
bond in ethane bond in ethane
#H H HL H
Nat —s ar,
a4 \ = Hep oH
u H oH
HOH H
wo
ve a a7"
HOH
H’ H
a HH
oo Ds
H H Ht iH
i
Staggered conformation is the most stable conformation of ethane whereas eclipsed is the least
stable conformation due to torsional strain.
Rotation about a carbon-carbon single bond is not completely free because of the energy difference
between the staggered and eclipsed conformers. The eclipsed conformer is higher in energy, so
an energy barrier must be overcome when rotation about the carbon-carbon bond occurs. However,
the barrier in ethane is small enough (2.9 keal mol or 12 kJ mol) to allow the conformers to
interconvert millions of times per second at room temperature. Because the conformers
interconvert, they cannot be separated. Figure shows the potential energies of all the conformers
of ethane obtained during one complete 360° rotation. Notice that the staggered conformers are
at energy minima, whereas the eclipsed conformers are at energy maxima.
‘eclipsed conformers
i ee ea 4-H
Potential enaray
¥ W
4. H 4, H i H
W 1H W H W 4
a H
staggered conformers
1 L 1 L 1
o oF Tae 180° 8 30
Degen of tation
Fig. Potential energy of ethane as a function of the angle
of rotation about the carbon-carbon bond.
Butane has three carbon-carbon single bonds, and the molecule can rotate about each of them. In
the following figure, staggered and eclipsed conformers are drawn for rotation about the C-1 —
C-2 bond. The carbon in the foreground in a Newman projection has the lower number.
126 | Stereochemistry CHEMACADEMY
1 2 Vs 4
CHy—CHy—CH,—CHy
butane
the CAC bond)
fa cacao bond |
#H. HH aH
rife deinen
on
SES] PT
SES cnneee] Serer eer
Although the staggered conformers resulting from rotation about the C-1—C-2 bond in butane
all have the same energy, the staggered conformers resulting from rotation about the C-2—C-3
bond do not have the same energy. The staggered conformers for rotation about the C-2—C-3
co in fa are shown below.
ae ony 45CCH,
* wr ped
a vo “EPL
. ee a
Conformer D, in which the two met groups are as far apart as possible, is more stable than the
other two staggered conformers (B and F). The most stable of the staggered conformers (D) is,
called the anti conformer, and the other two staggered conformers (B and F) are called gauche
(goesh”) conformers. (Anti is Greek for “opposite of”; gauche is French for “left.”) In the anti
conformer, the largest substituents are opposite each other; in a gauche conformer, they are adjacent.
The two gauche conformers have the same energy, but each is less stable than the anti conformer.
a
Anti and gauche conformers do not have the same energy because of steric strain. There is more
steric strain in a gauche conformer than in the anti conformer because the two methyl groups are
closer together in a gauche conformer. This type of steric strain is called a butane gauche
teraction.
The eclipsed conformers resulting from rotation about the C-2—C-3 bond in butane also have
different energies. The eclipsed conformer in which the two methyl groups are closest to each
other (A) is less stable than the eclipsed conformers in which they are farther apart (C and E).
The energies of the conformers obtained from rotation about the C-2—C-3 bond of butane are
shown in figure. (The dihedral angle is the angle between the CH;—C—C and C—C—CH,
planes. Therefore, the conformer in which one methyl group stands directly in front of the other—
the least stable conformer—has a dihedral angle of 0°.) All the eclipsed conformers have both
torsional and steric strain.
Stereochemistry | 127 MFJAM/ MSc. Entrance
ve
To a 3
theta ange
Fig. Potential energy of butane as a function of the degree of rotation about the
C-2—C-3 bond.
‘The relative number of molecules in a Particular conformation at any one time depends on the
Stabilty of the conformation: The more stable the conformation, the greater is the fraction of
molecules that will be in that conformation, Most molecules, therefore, are in staggered
conformations, and more molecules are in an anti conformation than in a gauche conformation.
The tendency to assume a staggered conformation eauses carbon chains to orient themselves in a
Zigzag fashion,
Effect of Interacting Groups on stability of conformers.
OH-CH, ~CH, -0H
(D Polar Solvent:
H
J
gn
H H
SH on HO, HOH
“iy, H ‘H
ya De
H H 60 oH HO 6
H H H H on
I i M1 I
(Most stable
1 sable)
Energy Order: IV 11> 1 >1
(ii) Non Polar Solvent:
OF oy OH
,, H
A *Q
H Ho, H
Ll i OH
FE. anti
H-bonding
Gauche
(Most stable)
128 | Stereochemistry % (CHEM ACADEMY
Order of Energy: F.E. > P.E. > Anti > Gauche
Stability: Gauche > Anti > PE. > FE.
(20) CYCLOALKANES: RING STRAIN
Bacyer predicted that cyclopentane would be the most stable of the cycloalkanes because its
bond angles (108°) are closest to the ideal tetrahedral bond angle. He predicted that cyclohexane,
with bond angles of 120°, would be less stable and that as the number of sides in the cycloalkanes
increases, their stability would decrease.
|o oO oO
(planar cydopentane “planar cydohexane “planar crdobeptane
Rondonercioe” —“bendangiers'ae—“Eondangles= HOE"
Contrary to what Baeyer predicted, cyclohexane is more stable than cyclopentane. Furthermore,
cyclic compounds do not become less and less stable as the number of sides increases. The
mistake Baeyer made was to assume that all eyclic molecules are planar. Because three points
define a plane, the carbons of cyclopropane must lic in a plane. The other eycloalkanes, however,
are not planar. Cyclic compounds twist and bend in order to attain a structure that minimizes the
three different kinds of strain that can destabilize a cyclic compound :
Angle strain is the strain induced in a molecule when the bond angles are different from the ideal
tetrahedral bond angle of 109.5°.
The bond angle in cyclopropane are compressed from the ideal bond angle of 109.5° to 60°, a
49.5° deviation. In cyclopropane, overlapping orbitals cannot point directly at each other. Therefore,
the orbital overlap is less effective than a normal C—C bond, causing angle strain. The C - C
bonding orbitals in cyclopropane have shape resembling bananas, thus often called banana bonds.
Likewise, in cyclo butane bond angle is compressed from 109.5° to 90° (associated with planar
ring), thus have less angle strain than cyclopropane.
2. Torsional strain is caused by repulsion between the bonding electrons of one substituent and the
bonding electrons of a nearby substituent.
3. Steric strain is caused by atoms or groups of atoms approaching each other too closely.
‘Although planar cyclobutane would have less angle strain than cyclopropane, it could have more
torsional strain because it has eight pairs of eclipsed hydrogens, compared with the six pairs of
cyclopropane. So cyclobutane is not a planar molecule—it is a bent molecule. One of its methylene
groups is bent at an angle of about 25° from the plane defined by the other three carbon atoms.
This increases the angle strain, but the increase is more than compensated for by the decreased
torsional strain as 4 result of the adjacent hydrogens not being as eclipsed, as they would be ina
planar ring.
If eyclopentane were planar, as Baeyer had predicted, it would have essentially no angle strain,
but its 10 pairs of eclipsed hydrogens would be subject to considerable torsional strain, So
cyclopentane puckers, allowing the hydrogens to become nearly staggered. Inthe process, however,
it acquires some angle strain. The puckered form of cyclopentane is called the envelope
conformation because the shape resembles a squarish envelope with the flap up.
(21) CONFORMATIONS OF CYCLOHEXANE
The cyclic compounds most commonly found in nature contain six-membered rings because
such rings can exist in a conformation that is almost completely free of strain. This conformation
is called the chair conformation. In the chair conformer of cyclohexane, all the bond angles are
Stereochemistry | 125 NTJAM/M.Sc. Entrance jacent bond:
111°, which is very close to the ideal tetrahedral bond angle of 109.5°, and all the adjacent bonds
are staggered. The chair conformer is such an important conformer that you should learn how to
draw it.
| H H a,
; etree ee cee
4 zl
ce
cs wenn
| 4 n 4
te torme :
| “Sanomest "srceackiime
1. Draw two parallel lines of the same length, slanted upward. Both lines should start at the same
height.
= Connect the tops of the lines with a 'V; the left-hand side of the V should be slightly longer than
the right-hand side. Connect the bottoms of the lines with an inverted V; the lines of the V and
the inverted V should be parallel. This completes the framework of the six-membered ring.
/ / £7
a) @)
3. Each carbon has an axial bond and an equatorial bond. The axial bonds are vertical and alternate
above and below the ring. The axial bond on one of the uppermost carbons is up, the next is
down, the next is up, and so on.
4, The equatorial bonds point outward from the ring. Because the bond angles are greater than
90°, the equatorial bonds are on a slant. Ifthe axial bond points up, the equatorial bond on the
same carbon is on a downward slant. and vice-versa
aioe _|
ert
Notice that each equatorial bond is parallel to two ring bonds (two carbons over) and parallel to
the opposite equatorial bond.
Cyclohexane rapidly interconverts between two stable chair conformations because of the
ase of rotation about its carbon-carbon bonds. This interconversion is known as ring flip.
[pull this
[carbon down
° ing flip
push thi a
[carbon up,
30 | Stereochemistry . CHEM ACADEMY
Fig. The bonds that are axial in one chair conformer are equatorial in the other chair conformer. The
bonds that are equator ‘one chair conformer are axial in the other chair conformer.
| flagpole hydrogens
om
HH
boat conformer of Newman projection of
cyclohexane the boat conformer
Fig. The boat conformer of cyclohexane, a Newman projection of the boat conformer,
showing that some of the bonds are eclipsed.
Cyclohexane can also exist in a boat conformation. Like the chair conformer, the boat conformer
is free of angle strain. However, the boat conformer is not as stable as the chair conformer
because some of the bonds in the boat conformer are eclipsed, giving it torsional strain. The boat
conformer is further destabilized by the close proximity of the flagpole hydrogens (the hydrogens
at the “bow” and “stern” of the boat), which causes steric strain.
‘The conformations that cyclohexane can assume when interconverting from one chair conformer
to the other are shown in Figure. To convert from the boat conformer to one ofthe chair conformers,
one of the topmost carbons of the boat conformer must be pulled down so that it becomes the
bottommost carbon. When the carbon is pulled down just a little, the twist-boat (or skew-boat)
conformer is obtained. The twist-boat conformer is more stable than the boat conformer because
there is less eclipsing and, consequently, less torsional strain and the flagpole hydrogens have
moved away from each other, thus relieving some of the steric strain. When the carbon is pulled
down to the point where it is in the same plane as the sides of the boat, the very unstable half-
chair conformer is obtained. Pulling the carbon down farther produces the chair conformer.
‘The graph in Figure shows the energy of a cyclohexane molecule as it interconverts from one
chair conformer to the other; the energy barrier for interconversion is 12.1 kcal mol (50.6 kJ
mol). From this value, it can be calculated that cyclohexane undergoes 10° ring flips per second
at room temperature. In other words, the two chair conformers are in rapid equilibrium,
“eeug ws,
half-chair \ f> halkechair
=
7. Ae wa
pa zai] [28% at
Fig. The conformers of cyclohexane—and their relative energies—as one
chair conformer interconverts to the other chair conformer.
Because the chair conformers are the most stable ofthe conformers, at any instant more molecules
of cyclohexane are in chair conformations than in any other conformation.
Stereochemistry | 131 NT-JAM/M Sc. Entrance
(22) CONFORMATIONS OF MONOSUBSTITUTED CYCLOHEXANES
Unlike cyclohexane, which has two equivalent chair conformers, the two chair conformers of a
monosubstituted cyclohexane such as methyleyclohexane are not equivalent.
Feet arpa
angst pan
Zz ener aran |
tng zs
LT chy sng tp ey mene
Hy
sore stable ass sa
chalrcontormer ‘ha conformer
Fig. A substituent is in an equatorial position in one chair conformer and in an
axial position in the other. The conformer with the substituent
in the equatorial position is more stable.
Sn
rea] We
nH a aH? H
ere
Figure An equatorial substituent on the C-1 carbon is anti to the C-3 and C-5 carbons,
‘Therefore the substituent extends into Space, away from the rest of the molecule.
Hoy cH bs #
4 Ch, BAe ci, A a
H Hy a
nn H H
I
a
methyl gauchetoC3] —_ [Inethyl in gauche to CF
Figure An axial substituent on the C-1 carbon is gauche to the C-3 and C-S carbons,
Therefore causing unfavourable steric interaction between the axial methyl group and both the
axial substituent on C-3 & C-5,
The chair conformer with the methyl substituent in an equatorial position is the more stable
conformer because a substituent has more room and, therefore, fewer steric interactions In other
words, the three axial bonds on the same side of the ring are parallel to each other, sa any axial
Substitvent willbe relatively close tothe axial substituents on the other two carbons, Beearss the
interacting substituents are on 1,3-positions relative to each other, these unfavorable steric
interactions are called 1,3-diaxial interactions.
1.3.x interactions
The gauche conformer of butane and the axiak-substituted conformer of methykeyelohexane are
compared in Figure. Notice thatthe gauche interaction is the same in both—an interaction betweeg
132 | Stereochemistry (CHEM ACADEMY
a methyl group and a hydrogen bonded to a carbon gauche to the methyl group. Butane has ane
such gauche interaction and methyleyclohexane has two.
ois o
He 4 H
1 W H
i hah
al
| sau butane imetykiherane
‘We saw that the gauche interaction between the methyl groups of butane caused the gauche
conformer to be 0.9 keat mol (3.8 kJ mol) less stable than the anti conformer. Because there are
two such gauche interactions iv the chair conformer of methylcyclohexane when the methyl
group is in an axial position, this chair conformer is 1.8 kcal mol (7.5 kJ mol) less stable than the
chair conformer with the methyl group in the equatorial position.
The substituent with the greater bulk in the area of the 1,3-diaxial hydrogens will have a greater
preference for the equatorial position because it will have stronger 1,3-diaxial interactions.
(3) CONFORMATIONS OF DISUBSTITUTED CYCLOHEXANES
Ifthere are two substituents on a cyclohexane ring, both substituents have to be taken into account
when determining which of the two chair conformers is the more stable. There are two different
disubstituted cyclohexanes, One has both substituents on the same side of the cyclohexane ring;
it is called the cis isomer (cis is Latin for “on this side”). The other has the two substituents on
opposite sides of the ring; it is called the trans isomer (trans is Latin for “across”). cis-1,4-
Disubstituted cyclohexane and trans-1,4-disubstituted cyclohexane are called geometric isomers
or cis-trans isomers : They have the same atoms, and the atoms are linked in the same order, but
they differ in the spatial arrangement of the atoms.
he two methyl groups are
[on oppasite sides ofthe ring
cH H
dis t4-dimethylogdohexane tran A-dimethykydobexane
Examples: (i) 1,4-dimethyleyclohexane
H : H
cH, cay
equatorial (eqatoray
#
bs bs
(aa dette
Both chair conformers are equally stable.
In contrast, the two chair conformers of trans-1,4-dimethylcyclohexane have different stabilities
because one has both methyl substituents in equatorial positions and the other has both methyl
groups in axial positions.
Stereochemistry | 133 UTJAM/M.Sc. Entrance
H
e
ce
Sra a
|e fh aaa)
morstale les sabe
trans-1.4-dimethykeyclohexané
The chair conformer with both substituents in axial positions has four 1,3-diaxial interactions,
causing it to be about 4 x 0.9 kcal/mol = 3.6 keal mol (15.1 kJ mol) less stable than the chair
conformer with both methyl groups in equatorial positions. We can, therefore, predict that frans-
1.4-dimethyleyclohexane will exist almost entirely in the more stable diequatorial conformation.
= \
i a
WW
bch one ar
tor toa rete
Gil) I-tertbutyl-3-methyleyclohexane
oR
i
mote #
| cere ek CHy
more stable is stable
ie erty. metiyeyahexane
* Both conformers of the trans isomer have one substituent in an equatorial Position and the other
in an axial position. Because the tert-butyl group is larger than the methyl 8roup, the 1,3-diaxial
interactions will be stronger when the tert-butyl group is in the axial Position. Therefore, the
conformer with the fert-butyl group in the equatorial position is More stable.
7
so instr Gee H
curf i. Zi-7* *
‘Crt CH
‘more stable less stable
trans-t-tertbutyl3.methyleyclohexane
* Hydrogen Bonding: Intramolecular hydrogen bonding between 1,3. iaxial OH groups in
nonpolar solvents confers appreciable stability of a conformer. In polar solvents, however, the
solvent competes for intermolecular H-bond formation, resulting in normal sterie effect dominating
the equilibrium,
areas 8
pee a a
nd
134 | Stereochemistry (24)
‘CHEM ACADEMY
CONFORMATIONS OF FUSED RINGS
‘When two cyclohexane rings are fused together, the second ring can be considered to be a pair of
Substituents bonded to the first ring. As with any disubstituted cyclohexane, the two substituents
can be either cis or trans,
Tf the cyclohexane rings are drawn in their chair conformations, the trans isomer (with one
substituent bond pointing upward and the other downward) will have both substituents in the
equatorial position.
The cis isomer will have one substituent in the equatorial position and one substituent in the
axial position. .
‘Trans-fused cyclohexane rings, therefore, are more stable than cis-fused cyclohexane rings.
oa
tranedcsin diedecain
‘wanted cofened rng
vores Tesrrtable
Stercochemistry | 138 ITJAM/M.Se. Entrance
EXERCISE - I
Single Correct Type a
In3 chloro-2 methyl pentane the priority sequence for fixing the R and S configuration is :
(@) —(CH,),CH,—C,H —ClH_ (bt) (CH,),CH, —Cl, —C)Hs, H
()—C,—(CH,),CH, —CH,,H (4) Cl, —C,H,, —(CH,),CH, H
The absolute configuration at the two chiral centres in D-ribulose are
on |
fon!
| p-xitlose |
(©) 38, 4R (d) 38, 4S
(a) 3R, 4R (0) 3R, 4S,
In the following reaction,
Ho
on MN X+Y
ence (iastereomers)
A yerddeyse
the absolute configurations of the chiral centres in X and Y are
(a) 2S, 3R and 2R, 3R (b) 2R, 3R and 2R, 3S
(c) 2S, 3S and 2R, 3R (@) 28, 3R and 28, 3R
The structure of an optically active isomer of 2 methyl cyclopentanol is shown below
Qe
‘OH
The absolute configuration of this isomer is
(@) IR, 2R (b) 1s, 28 (©) 18,28 (@) IR, 28
What isthe absolute configuration ofthe following moleules? (NS= the molecule has no center)
Note: For the purpose ofthis question only, the order of stereocenters isnot specified; ie, RS
cl
HOS fay ay ay
a
H,C=Ny HC=NH
Pr Br
av) BX/
cl
1 rom w 1 1 om w 5
@ R RS R NS () R RRS RR
© R RS NS NS @ R SRR. RS
136 | stereochemistry ‘CHEMACADEMY
How many chiral center (excluding N centres) are there in morphine?
‘CH3
(a4 ©6 (d) More than 6
CH, - OH CH, - OH CHO
H-+-0H HO--H H--OH
@HO--H =) HO-++-H = © H-}-cH,On
cHO CHO OH
(@) & (L) configuration of above carbohydrate is
(aL, L,D (b) L,D,L OLLL (@)L,D,D
The stereachemistry of this molecule is:
CH; H
H cl
(a) IR, 3R (b) IR, 3S (©) 18,38 (@ 1S, 3R
What are the configurations (R or S) of the chiral centers in the following molecules:
H /OH ‘NH,
«y Hooc-En, gy “EY oS Y '
SH
(a) Compound 1 =
(b) Compound 1 =
; Compound Compound 3 = 18, 2S
; Compound 2 = S; Compound 3 = 1S, 2S
(c) Compound 1 = S$; Compound 2 = S; Compound 3 = 18, 2R
(4) Compound 1 = R; Compound 2= R; Compound 3 = 1S, 2R
The Cahn-Ingold-Prelog (CIP) priorities of the groups and the absolute configuration (R/S) of
the following compound are
OH
‘ ae
aortic” Soa,
(a) CH,OH > CH(CH,), > CH = CH, > CH, and S
(b) CH,OH > CH = CH, > CH(CH,), > CH, and S
(c) CH,OH > CH= CH, > CH(CH,), > CH, and R
(@ CH,OH > CH(CH,), > CH = CH, > CH, and R
Stereochemistry | 137 NFJAM/M.Sc. Entrance
i.
The structure of D-galactose is
CHLOH
H
CH,OH CH,OH CH,OH CH,OH
After the following interchanges of groups in the Fischer projection of 2-bromobutane, the
configuration of (X) and (¥) will be
Bi cn,
Fy > ube > wpe,
GHs bud) Br
@&) YY)
@X=RSY=8 ()X=R;Y=R (X=8;Y=R (X=5;
Total number of chiral centre present in the given compound is
©
re
(a4 ()5 @6 @7
—> L
HCL cH, HC 7
c=c=c=c% C=C=c=c
7 A \
H CH.
Tand II are geometrical isomers of each other because
@h=h ()4>1,
©h>1, (@/, and /, cannot be compared
Assign double bond configurations to the following:
OH
‘cH,0n
NC,
HN-cH, tN
(aE (yz OEE (@)Z,Z
138 | Stereochemistry / (CHEM ACADEMY
Fischer form of the following compound is
CH
H--0H HO-}-H te
HBr (BH © HBr W@H
CH; CH; CH;
Among the following structures, select E isomers (arrows indicate Ea bonds to be considered)?
CH. Br
F Ox,
w wh Ay (2) HCO"
iy
5
-0 \ CH;
HC
CH; Cl
Hew 4
(3) BC. \
cH;
(a) 1 and2 (b) 1 and 3 (©) Land 4 (@ 2and 3
Which of the following is E isomer?
What is the configuration of these two compound
Hy Br HAC
"OO Ors OO
CH
a eee (o)trans, trans (d) trans, cis
Stereochemistry | 139 ITJAM/ MSc. Entrance
20.
25.
Which of the following will not show geometrical isomerism.
Me ic =
o< >< © © cl @)
Which of the following will show geometrical isomerism.
ye
@ SO © ©, Sor “ @ D~<]
Which of the following compound can show geometrical isomerism.
Br, Ch 1H;
N, CH;
cae C:
(@ Fe (b) Nc,
F. Et Hi
Neue CHy ACH
(C=C C.
oO aaNet ® chy cH;
‘The geometrical isomerism is shown by
CH CH cH!
@ _o CO © @
cHCI
ane “ rN 4
Statement 1; a and ms are structural i s.
cu Nw Be Nou, ral isomers.
Statement 2: The above mentioned compounds can show geometrical isomerism,
(6) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
1. ~
(6) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1,
(c) Statement-1 is false, statement-2 is true,
(d) Statement-1 is true, statement-2 is false.
Tetracyline is called a broad spectrum antibiotic because it active ‘against a wide variety ofbacteria,
How many chirality center does tetracyline have?
ty
Ch on Nica,
HT
OH O on O
(a)3 (b)4 (5 @6
140 | Stereochemistry CHEM ACADEMY
HC
26. i
me This compound shows:
(@) geometrical isomerism (b) optical isomerism
(© both (d) none
Q
27. Statement-1: tautomer of this compound can show geometrical isomer.
&
OH
Statement-2 : across the double bond both the terminals having different groups.
(a) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
5
(b) Statement-I is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(©) Statement-1 is true, statement-2 is false.
(A) Statement-1 is false, statement-2 is true.
28. Statement-!
: E-cyclopentadecene is having more AH, (Heat of combustion) than Z isomer.
Statement-2 : E-cyclopentadecene is more stable than Z isomer.
(a) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-.
(b) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(c) Statement-I is true, statement-2 is false.
(q) Statement-1 is false, statement-2 is true,
29. Which of the following molecule is achiral
HG ou Ha, ft
o faery ay fp=c=c=q
H ‘Hs H ‘Br
ON COOH
Br
an ", av) ©) ©
cl HOOC NO2
@l (by ul @IV
30. Which compound does not posses a plane of symmetry
HOH
Fi cy
@ ay Q am) ay)
FF CH; CH
Br H
Stereochemistry | 141 NT-JAM/M Se, Entrance
31.
32,
33.
34,
36.
(@)1,MandIV — (b)MandIIT_ (cM andIV.—(d) None of these
Which of the following compound are optically active
ay ad ac ay ne
=C=CH 2C=C=" ‘2C=C=0
© peace ay Se (MD ,2C=C=CN
a= OCH,, b=NHCOCH,, C= CH,, d= CH,CH,
(@) only (b) Ill only (©) Land Ill (d) Mand IIT
The binapthol is
OO...
OH
@e)
(a) an optically active compound having chiral centre
(b) an optically inactive compound
(©) ameso compound
(4) an opticaly active compound without having chiral centre
Which of the following is correct the given compound
°
OOO
oO O ‘O
(@) It posses a centre of symmetry _(b) It posses C, axis of symmetry
(© Posses the plane of symmetry (d) Compound is chiral
Which of the following compound is optically active
scl wel HAC, CH;
»® ® J © ao
Gy cr CH; HC
Among the following molecule, which one is chiral?
Br. Br
[es Bi
@ LZ T (b) Dam po " (d) Ao
Which of the following molecules is chiral
o® OH (1D Ho
OH COOH
(aI © @LU
142 | Stereochemistry (@) chiral
(©) Optically active
38. — Which of the following is achiral?
HAC
89
CH,
(@) HC ‘CH?
a
o
g
%c
oO
CH)
(©) H2C ‘CH
HO,C
39.
Hy
cl
QO)
cl
HO,S
CH;
HC.
oS! © ©)
4
(CHEM ACADEMY.
(0) C, axis of symmetry
(@ All of these :
"Or
(b) Hac
CH;
HO,C
OO
5
Which of the following structure would not rotate plane polarized light?
CH.
Cl. HL. Ka
» QO
CH,
c
SO.H
Hy
Hoe ,
40. Which of following compound is achiral?
(@) Me \-o
F
°
g
HL Z ;
© (@) All of these
a Br, H
Stereochemistry | 143 UTJAM/M.Sc. Entrance
41.
42.
43.
Select the optically active compound among the following :
Statement 1 — A is optically active and B is optically inactive.
Statement 2— A has a centre of symmetry
(a) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
1 .
(b) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(©) Statement-1 is false, statement-2 is true.
(d) Statement-1 is true, statement-2 is false.
‘What are the elements of symmetry present in the following molecules and which of them is
chiral?
c A B
(a) A has a 2-fold rotation axis and B has a plane of symmetry; A is chiral
(b) A has a plane of symmetry and B has a centre of inversion; B is chiral
(©) Ahas a plane of symmetry and B has a 2-fold rotation axis; A is chiral
(4) A has a plane of symmetry and B has a 2-fold rotation axis; B is chiral
Which one among the following molecules is chiral?
cl HH cl H
@ cy c=c={
a cl H cl
144 | Stereochemistry 45.
46.
47.
48.
49.
50.
CHEMACADEMY
acl,
cl cl
2 vo, a nw)
clu
Among the following, the correct statement concerning the opticaly activity is
(@) a molecule containing two or more chiral centres is always optically active
(b) a molecule containing just one chiral centre is always optically active
(©) a molecule possessing alternating axis of symmetry is optically active
(d) an optically active molecule should have at least one chiral centre
The achiral molecule among the following. is
a, fl
a.
H H
Ca
© fore
Which of the following molecules are chiral?
CH;
HO. cH; ¢ cl
cl
oy yg 7 » DO. mo a
H _
(a) 1,1, Mand IV (b) 1, and IV (c) Hand IV (@) land
Which of the following does not possess any element of symmetry?
(a) Ethane (b) (+) tartaric acid
(c) Carbon tetrachloride (d) Mesotartaric acid
The compounds given below are :
5 §
Coon Coon
(a) Enantiomers (b) Identical (c) Regioisomers (d) Diastereomers
The molecule(s) that exist as meso structure(s)
D070
K L M
is/are
(a) only M (b) both K and L_ (¢) Only L (d) only K
Stereochemistry | 145 UFJAM/M.Sc. Entrance
Si.
52.
a3.
54,
55.
. OH; replace Ha with D and Hb with H a
H-}-Hb
a Gs replace Hb with Dand Ha with ()
relation between (X) and (Y) is
(a) Enantiomers (b) Diastereomers
(©) E and Z isomers (@ Constitutional isomers.
Molecules shown are
3,
vy, VW
F H
(a) Constitutional isomers (b) Enantiomers
(©) Diastereomers (@) Identical
The molecules shown are
CH CH;
(a) Enantiomers (b) Diastereomers
(©) Constitutional isomers (d) Non isomers
Esterification of the acid P with the alcohol Q will give
“chs oa
coor owe
(SP @eo
(a) only one enantiomer (b) a mixture of diastereomers
(©) a mixture of enantiomers (@) only one diastereomer
The molecules shown are
u 8
Hi Pe—H
oir mi
oe ee
a 3 .
(a) Constitutional isomer (b) enantiomers *
(c) Diastereomers (d) Identical isomers
146 | Stereochemistry 56.
ee
58.
nee
61.
CHEM ACADEMY
Relation between these two. compound is
Reh
(a) constitutional isomer (b) Enantiomers
(©) Identical (d) Diastereamers
Relation between-these two compound is
BOBS i
HY “0H 8 You
(@) Enantiomers (by Diastereomers (¢) Identical (4) Constitutional isomers
‘What is the relation between these two compounds
wort = and we ames
(a) Enantiomers (b) Diastereomers (c) Identicals _ (d) None of these
Which of the following pair of compound is a pair of enantiomers
a Br ey
Or oman".
ca a
cl cl
© Ch CK ory wy
ad oc a c
The following compound differ in respect of
no Hos sOH
HO “OH Ho” OH
OH OH
(a) their chemical and physical properties
{b) nothing
(c) the direction in which they rotate plane of polarization light
(q) their interaction with molecules
The two compounds shown below are:
H
°. SH AH oo
on and aS
(a) diastereomers (b) enantiomers (c) epimers (d) regiomers
Stereochemistry | 147 UT-JAM/M.Sc. Entrance
62.
63.
65.
66.
coa aoa
@) (b) oC
Br Br Br Br
Relationship between above pair (a) & (b) is
(@) Enantiomer (b) Diastereomers (c) Identical (4) Structural isomer
Meso-tartaric acid and d-tartaric acid are
(@) positional isomers (b) enantiomers
(c) diastereomers (d) racemic mixture
‘The structures shown here are related as being:
* cH, Br
CHy ch, HY,
Br 4
qa)
(a) conformers (b) enantiomers
(© geometrical isomers (A) diastereoisomers
Which out of the following are resolvable.
H, H
@ PL YOM gy own © AN @ De
H Hy CH Hy OH
(00H
The correct sequence of relationship between the compounds of the following pairs isiv is
CH;CH, CH;
COOH CHs H--Br HBr
@ H-ENH, ENE (i) Br>-H —Br--H
CH3 COOH CH; CH,CH;
Ph CH; CH)CH3 CH;
Ho--H- H—-ENH, H--Cl ClI--H
Gi) HN--H Ho-+H (vy) HBr Br—-H
CH; Ph CHy CH,CH3
(a) Identical, enantiomers, diastereomers and structural isomers
(b) enantiomers, identical sttructural isomers and diastereomers
(c) enantiomers, identical diastereomers and structural isomers
(d) identical, identical, diastereomers and structural isomers
148 | Stereochemistry 67.
68.
69.
70.
ae
CHEM ACADEMY
‘What is ‘ic
al a relation between of n-butane having dibydral angle are ® = 60° and 6 = 300°
5
CH:
H H H
H tt 7
g= 60° q=300°
(@) Enantiomers (b) Diastereomers (c) Identicals. (d) None of these
The following compounds are identical with respect to:
ct" ; acy
cl
,,
‘cl
(a) Molecular composition (b) boiling point
(©) melting point (A) IUPAC name
Identify diastereoisomer in the following are :
. cn cH cl
ci—}—cx, 4 _ ee x
® q—t —cH, 4 © cH—-—H CH
H CH, a 7
CH, cH, sa
H. cl H cl 1H,
H—}— cl {San
On cl. SP a ow
ClCH.
cH, cH, cH, 7
Which of the following compound has one of the stereoisomers as a meso compound?
QO od wor at
‘Number of possible 3D-isomers (stereoisomers) of glucose are
(a) 10 (b) 14 (o)16 (420
‘The number of cis-trans isomer possible for the following compound
C~h
(2 4 (6 @8
Stereochemistry | 149 NT-JAM/MSc. Entrance
73.
74,
75.
76.
71.
28.
79.
80.
8i.
Total number of geometrical isomer of following compound is:
(@)2 (b)3 (4 @5.
Total number of geometrical isomer of following compound.
AADAAD
(a)2 (b)4 ©s8s (d) 16
The maximum number of stereoisomers possible for 4-phenylbut-3-en-2-0l is
@1 (b)2 ©3 (d)4
The number of enantiomers of camphor
0
(a) Four (b) Three () Two (d) One
How many structural isomer are possible when one of the hydrogen is replaced by a chlorine
atom in anthracene?
(a)3 (b)7 ()4 (d)6
How many structural isomers of CjHj9 are possible.
@10 (1 (©) 12 @2B3
C,H,CI shows how many benzenoid aromatic isomers 2
(a4 (b)3 (5 @6
The molecular formula of diphenylmethane,
Hy ;
c risC Hs
How many structural isomers are possible when one of the hydrogen is replaced by a chlorine
atom?
(a6 (b)4 (c)8 (@)7
The number of all the possible stereoisomers formed by the given compound is:
(a2 (b)3 (©) 32 (a) 64
150 | Stereochemistry 82.
83.
85.
86.
87.
88.
89.
CHEM ACADEMY
The compound if contains an even number ‘n’ of chiral carbons, but the molecule can be divided
into two equal and similar halves, then how many optical active form it will have :
j@2 (by 20-D (20-22 () 20-D-20-12
Ifthe molecule having 60% optical purity of S enantiomer. What should be the total % of S and
R enantiomer are present in the solution
(@) 20% of S and 80% of R (b) 60% of S and 40% of R
(©) 80% of S and 20% of R (@) 40% of S and 60% of R
Most stable conformation of 2-methyl butane is
CH; GAs
H CH; Hi
@ HSC H (b) ne
H Be Ww
cH, CHy
HC. H CH;
© @ H
H3C H Ho SH
Which of the following compounds is most stable?
oT no oa OLIN
Pure (S)-2-butanol has a specific rotation of +13.52 degrees. A sample of 2-butanol prepared in
the lab and purified by distillation has a calculated specific rotation of +6.76 degrees. What can
you conclude about the composition?
(a) 50% (S), 50% impurity (b) 50% (S), 50% (R)
(© 50% (S), 50% racemic (@) Some other mixture
Gs CH;
HE. no
Optical rotation produced by Cl—F—H {is 36° then that product by H
CH CH;
(@)-36° (wo (©) 436" (d) unpredictable
Isomers which can be interconverted through rotation around a single bond are
(@)\Conformers (b) Diastereomers (c) Enantiomers (4) Positional isomers
One of the configuration of n-butane is drawn in the given figure. Anticlockwise rotation of C,
around C,-C; bond by 120° will lead to
Hs
H
H
Hs
(a) gauche (b)staggerred _(c) partially eclipsed (d) fully eclipsed
Stereochemistry | 151 HT-JAM/M.Sc. Entrance
90,
91.
92.
cee
94,
95.
In the given conformation, if C, is rotated about C,-C, bond anticlockwise by an
angle of 120° then the conformation obtained is
én,
H. ve
b
nH?
ICH,
(@) fally eclisped conformation (b) partially eclipsed conformation
(c) gauche conformation (d) staggered conformation
Tn which of the following has minimum torsional strain and minimum Vander waal
strain.
AK HX
(aI (b) (©) TI (d@)IV
9
HO-CH,-CH, aoe H
o a ®
Which conformer of above compound is most stable
(consider conformer across (C, -C;))
(a) Staggered (b) Gauche
(©) Fully eclipsed (d) Partially eclipsed
Increasing order of stability among the three main conformation (i.e. eclipse, anti,
gauche) of ethylene glycol is (in gas phase) :
(a) Eclipse, gauche, anti (b) Gauche, eclipse, anti
(c) Eclipse, anti, gauche (d) Anti, gauche, a
‘Which of the following form stable for OH - CH, ~ CH, -
(a) staggered form (b) Partically a
(©) Gauche form (d) Eclipsed form
Which is the most stable confermer of glycol in H,O
(a) anti (b) gauche (©) eclipsed (@) fally eclipsed
152 | Stereochemistry 96.
97.
98.
100.
101.
. . (CHEM ACADEMY
‘Which of the following pairs of structures represent conformational isomers?
ODAm AJ ODA mt Dh
© 7S and
Conformational changes in a molecule leads to. change in
(a) torsional angle (b) borid angle
(©) bond length (@) all of the above
Identify the stable conformation of pentane
nc7H cots
H CH, H, H
(a) )
H H H ‘CH;
H H
CH
nyc“ nce
H H Hs
(d) H
On H i Ly,
CH, H
Which should be the most stable form of cyclohexane
ex}! whK4A ef7 od
Which of the structure wilt be produced if'a ring flip occure in the following compound in chair
‘aa
@viyr oP 0 Fr oky
Which is the most stable chair form of this compound?
TOL
oy ©) ve oA Aeoyh
form.
Stereochemistry | 153 UFJAM/MSc. Entrance
102.
103.
105.
* 106.
154
The most stable conformation of the following compound is:
tBu ee ane le
b
w Me © py expe
tBu tT Me
Bu
© (@) H
H Me Me
The stable form of trans 1,4-dimethyl cyclo hexane is represented by
CH;
CH;
ee ny
CH;
a 7~ cH,
© HyC_L~7~cn, ol
b
Among the following, the most stable isomer is
OH
(@) Z~T-on, ()
HO OMe
OMe OH OMe
© Ly, ® pL)
OH
‘What is the relationship btween the two structures shown?
cH; GI
cn. L7~cH, me)
(a) Constitutional isomers (b) Stereoisomers
(c) Different drawing. of the same conformation of the same compound
(4) Different conformation of the same compound
When cyclohexane is poured on water, it floats, because:
(a) cyclohexane is in ‘boat’ form —_(b) cyclohexane is in ‘chair’ form
(©) cyclohexane is in ‘crown’ form (4) cyclohexane is less dense than water
‘Stereochemistry (CHEM ACADEMY
107. Among the structure shown below, which are lowest potential energy?
®©LL ry © Q «Y=
108. The pair of conformation that has maximum energy difference is
@ Xam ) Aan vA
ofa oAauwW
109. The correct stability order of the following species is
H H fe
le HL, Me
Zoe poe Sec
(a) H H Me
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