BIOCHEM

ISOMERS AND ENANTIOMERS

LINKS: enantiomer isomerism and enantiomers part 1 Isomerism and enantiomers part 2

ISOMERS

STEREOISOMERS
➔ CONNECTIONS ARE THE SAME TO THE ATOMS BUT ARE
DIFFERENT IN THE WAY THEY ARE ARRANGED
➔ THE 3D STRUCTURE OF THESE MOLECULES AND POSITION
OF THE GROUPS ARE DIFFERENT

A. CONFORMATIONAL ISOMERS
● TWISTING OF THE BONDS SO THAT THE MOLECULE ITSELF
WILL HAVE DIFFERENT FORMS
● PREFER THE LEAST ENERGY POSITION; PREFER ONE
WHERE ALL THE ATOMS HAVE SPACE FOR LESS STERIC
HINDRANCE
● AS THEY TWIST AROUND THEY HAVE DIFFERENT
CONFORMATIONS

CONSTITUTIONAL/STRUCTURAL ISOMERS B. CONFIGURATIONAL ISOMERS

➔ THEY HAVE THE SAME MOLECULAR FORMULA BUT THEY ● DIFFERENT MOLECULES / THEY ARE NOT THE SAME
HAVE CONNECTIONS ALTOGETHER
MOLECULES
➔ STERIC HINDRANCE
- BECAUSE OF THE INTERACTIONS OF THE ATOMS, THEY
1. GEOMETRIC
PUSH AND REPEL AGAINST EACH OTHER
● POSITION WHERE GROUPS ARE DOUBLE BONDED
- THE SLOWING OF CHEMICAL REACTIONS DUE TO STERIC
BULK. IT IS USUALLY MANIFESTED IN INTERMOLECULAR
REACTIONS

STERIC HINDRANCE IS VERY HIGH

MOLECULES DOES NOT LIKE THIS POSITION
(LESS COMFORTABLE, HIGH ENERGY)

❖ CIS CONFIGURATION
- ARE WHEN GROUPS ARE ON THE SAME
POSITION/SIDE OF DOUBLE BONDS
❖ TRANSE CONFIGURATION
- ARE WHEN GROUPS ARE ON THE OPPOSITE SIDE

HYDROGENS ARE FARTHER APART, SO LESS HINDRANCE

IN COMFORTABLE POSITION (IN LOWER ENERGY)
 LESSON # 3

2. OPTICAL MOLECULAR CHIRALITY: ENANTIOMERS

● BIOCHEMICALLY IMPORTANT; HAS AN IMPORTANT
DISTINCTION ENANTIOMERS
● ALTHOUGH THEY MAY CONTAIN THE SAME ATOMS
CONNECTED, IF THEY HAVE DIFFERENT ARRANGEMENT IN ➔ NON-SUPERIMPOSABLE MIRROR IMAGE ISOMERS
SPACE THEN BIOCHEMICALLY, THEY MAY NOT FUNCTION (THEY HAVE SYMMETRY)
➔ THEY ARE ALMOST THE SAME EXCEPT THEY HAVE
DIFFERENT ARRANGEMENT OF MOLECULES TO ITSELF
➔ ENANTIOMERS ARE RELATED TO EACH OTHER MUCH
LIKE A RIGHT HAND IS RELATED TO A LEFT HAND

❖ ENANTIOMERS
- STEREOISOMERS THAT ARE MIRROR IMAGES OF
EACH OTHER THAT ARE NOT SUPERIMPOSABLE
❖ DIASTEREOISOMERS
- HAS MORE THAN ONE CARBON THAT IS THE
CENTER WHERE DIFFERENT GROUPS ARE ➔ ENANTIOMERS HAVE IDENTICAL PHYSICAL
CONNECTED PROPERTIES, I.E., BP, MP, ETC.
- STEREOISOMERS THAT ARE NOT MIRROR IMAGES ➔ CHIRALITY (FROM THE GREEK WORD FOR HAND).
OF EACH OTHER ENANTIOMERS ARE SAID TO BE CHIRAL.

STEREOCHEMISTRY
➔ THREE-DIMENSIONAL ARRANGEMENT OF ATOMS (GROUPS) THE CHIRALITY CENTER
IN SPACE
➔ AS LONG AS IT HAVE FOUR DIFFERENT GROUPS ATTACHED

STEREOISOMERS TO A CARBON THEN YOU HAVE A CHIRAL CENTER

➔ MOLECULE WITH THE SAME CONNECTIVITY BUT DIFFERENT ➔ A MOLECULE CONTAINING A CARBON WITH FOUR

ARRANGEMENT OF ATOMS (GROUPS) IN SPACE DIFFERENT GROUPS RESULTS IN A CHIRAL MOLECULE, AND
THE CARBON IS REFERRED TO AS A CHIRAL, OR
ASYMMETRIC, OR STEREOGENIC CENTER.

★ MOLECULES ARE NOT CHIRAL IF THEY CONTAIN A PLANE

OF SYMMETRY: A PLANE THAT CUTS A MOLECULE IN HALF
SO THAT ONE HALF IS THE MIRROR IMAGE OF THE OTHER
HALF. MOLECULES (OR OBJECTS) THAT POSSESS A
MIRROR PLANE OF SYMMETRY ARE SUPERIMPOSABLE ON
THEIR MIRROR IMAGE AND ARE TERMED ACHIRAL.

GEOMETRIC ISOMERS (DIASTEREOMERS)

BIOCHEM 2
 LESSON # 3

CHIRAL CENTER ★ THE TWO ENANTIOMERS ARE RELATIVELY THE SAME

IN CHEMICAL PROPERTIES EXCEPT FOR OPTICAL
ENANTIOMERS: NON-SUPERIMPOSABLE MIRROR IMAGE ISOMERS ACTIVITY

OPTICAL ACTIVITY
➔ ONE OF THE WAYS TO DISTINGUISH THE TWO
ENANTIOMERS
➔ MOLECULES ENRICHED IN AN ENANTIOMER WILL ROTATE
PLANE POLARIZED LIGHT ARE SAID TO BE OPTICALLY
ACTIVE.

POLARIMETER

PLANE POLARIZED LIGHT: LIGHT THAT OSCILLATES IN

ONLY ONE PLANE

➔ THE OPTICAL ROTATION IS DEPENDENT UPON THE

SUBSTANCE, THE CONCENTRATION, THE PATH LENGTH
THROUGH THE SAMPLE, AND THE WAVELENGTH OF
LIGHT.
SYMMETRY IN ACHIRAL STRUCTURES
➔ ANY MOLECULE WITH A PLANE OF SYMMETRY OR A
CENTER OF SYMMETRY MUST BE ACHIRAL.
HOW TO REPRESENT:

LINEAR ALKANES:
- YOU SHOULD DRAW THE CARBON BACKBONE IN THE
ACHIRAL PLANE OF THE PAPER, AND DRAW SUBSTITUENTS
EITHER COMING TOWARDS YOU (WITH WEDGES) OR
GOING AWAY FROM YOU (WITH DASHES). NOTE THAT
EACH CARBON SHOULD LOOK LIKE A TETRAHEDRON.

CHIRAL

BIOCHEM 3
 LESSON # 3

FISCHER PROJECTIONS
- YOU WILL POSITION THE TWO GROUPS IN THE VERTICAL
POSITION AS THE BONDS GOING TOWARDS US
- REPRESENTATION OF A THREE-DIMENSIONAL MOLECULE AS
A FLAT STRUCTURE. A TETRAHEDRAL CARBON IS
REPRESENTED BY TWO CROSSED LINES:

BRIEF REVIEW

ISOMERS
- COMPOUNDS WITH THE SAME CHEMICAL FORMULA, BUT
DIFFERENT ARRANGEMENT OF ATOMS
CONSTITUTIONAL ISOMER
HAVE DIFFERENT CONNECTIVITIES (NOT LIMITED TO ALKANES)

STEREOISOMERS
- ATOMS CONNECTED IN THE SAME WAY, BUT DIFFERENT
THREE-DIMENSIONAL ARRANGEMENT OF ATOMS OR
GROUPS (TOPOLOGY)

I. ENANTIOMERS: NON-SUPERIMPOSABLE MIRROR IMAGE

ISOMERS
II. DIASTEREOMERS: NON-SUPERIMPOSABLE, NON-MIRROR
IMAGE ISOMER (MORE THAN ONE CHIRAL CENTER.
III. GEOMETRIC ISOMERS (DIASTEREOMERS): E / Z ALKENE
ISOMERS

BIOCHEM 4