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Curly arrows and stereoselectivity in organic
reactions
Student worksheet: CDROM index 23SW
Discussion of answers: CDROM index 23DA
Topics Curly arrows, the mechanism for esterification, inversion during SN2 reactions, saw-horse representations and stereoselectivity in elimination reactions.
Level Very able post-16 students.
Prior knowledge Curly arrows in organic mechanisms, nucleophilic attack, electrophilic attack and optical isomerism.
Rationale ‘All practising chemists protect themselves from being crushed by the vastness of organic chemistry by moulding it and ordering it with curly arrows. Without curly arrows, chemistry is chaos, and impossible to learn. Curly arrows unify chemistry, and are essential to the solution of problems’^1_._
Organic chemistry is sometimes presented to students with the emphasis on facts to recall rather than the underlying principles. Very able students tend to be interested in fundamental concepts and put off by a ‘just learn it’ approach. This activity explores some of the intellectually satisfying aspects of organic chemistry. The first part develops the use of curly arrows. If you have some very able students in a group, then there is a ready made opportunity for differentiation by giving them a chance to draw curly arrow mechanisms for whatever reactions they meet.
Evidence from the UK qualifying competition for the International Chemistry Olympiad
suggests that even very able students get little practice in presenting the three-dimensional shapes of molecules. This activity gives the students an opportunity to develop those skills.
Use This activity requires a good background knowledge of organic chemistry and should be used with students towards the end of their organic chemistry course. It can be given to the most able students in a group to work through independently. They should also be given the Discussion of answers sheet to review their progress. Students should be able to assemble simple 3D molecular models (such as Molymod®) when they are doing this activity.
(^1) Clayden, Greeves, Warren and Wothers, Organic Chemistry , Oxford: Oxford University Press, 2001.
Student worksheet 23SW Curly arrows and stereoselectivity in organic reactions
Stereoselectivity This refers to the tendency of some organic reactions to produce one stereoisomer in greater abundance or in exclusion to another.
S N 2
S N 2 reactions actually occur with an inversion of the stereochemistry at the electrophilic centre. The effect is a little like an umbrella being blown inside out in a strong wind. This happens because the nucleophile has to attack the carbon from directly behind the bond with the leaving group.
- Draw the products of the following substitutions:
continued on page 3
HO–^ I
a)
b)
H 3 N
HO–
- Fill the gaps in this cyclic set of reactions: (OH is not a good leaving group. It can be converted to a group given the label OTos which is a good leaving group.)
continued on page 4
Student worksheet 23SW Curly arrows and stereoselectivity in organic reactions
[α]D= +31°
TosCl pyridine
(+)-1-phenyl-2-propanol
[α]D= +33°
H 2 O/HO
CH 3 COO–
TosCl pyridine
(–)-1-phenyl-2-propanol [α]D= –33°
[α]D= –7°
[α]D= +7° [α]D= ..............°
CH 3 COO–
OTos
OH
a) Explain why the major product of the E 2 reaction is the trans isomer and the cis isomer is only a minor product.
b) Re-draw the mechanism to best show how the selectivity arises.
Student worksheet 23SW Curly arrows and stereoselectivity in organic reactions
HO–(alcohol) major product
minor product
Discussion of answers 23DA Curly arrows and stereoselectivity in organic reactions
Curly arrows and stereoselectivity in organic reactions
Curly arrows
1. Draw a curly arrow mechanism for the acid catalysed esterification of ethanoic acid and _ethanol.
- How could isotopic labelling be used to give supporting evidence for the proposed mechanism?_
The diagram below proposes a curly arrow mechanism for the acid catalysed esterification. The acid catalysis works by making the carboxylic acid much more susceptible to nucleophilic attack. The protonation is drawn here as a separate initial step, but could be drawn as part of a concerted step including nucleophilic attack by the ethanol.
The diagram illustrates the experiment that was done with ethanol containing the 18 O isotope. All the 18 O went into the ester and not into the water product.
H+^ + H 2 O
continued on page 2
Discussion of answers
+ H 2 O
4. Fill the gaps in this cyclic set of reactions:
TosCl is tosyl chloride. OTos is a much better leaving group than OH and can therefore be more readily substituted by the nucleophile.
[ α]D is a measure of the angle through which a certain quantity of the compound in solution rotates the plane of polarised light.
continued on page 4
Discussion of answers 23DA Curly arrows and stereoselectivity in organic reactions
[α]D= +31°
TosCl pyridine
(+)-1-phenyl-2-propanol
[α]D= +33°
H 2 O/HO
CH 3 COO–
TosCl pyridine
(–)-1-phenyl-2-propanol [α]D= –33°
[α]D= –7°
[α]D= +7° [α]D= –31°
CH 3 COO–
OTos
TosCl
Eliminations
5. By building a model of ethane and looking down the C-C bond while turning the CH 3 group (or otherwise), predict which conformation of ethane is more stable. State your reasons why.
The staggered conformation is the more stable because the hydrogens (and bonding electrons) have more room - they are less squashed together. The rationale behind this is similar to the valence shell electron pair repulsion (VSEPR) theory used to explain molecular shape.
Although the staggered conformation is the more stable, do not get the impression that we have lost free rotation between the two. The difference in energy between the two conformations is roughly 12 kJ mol-1. At room temperature the molecules have sufficient energy for the CH 3 groups to rotate. If very bulky groups are substituted instead of hydrogen then the difference in energy between the conformations is higher and likewise the temperature below which they stop inter-converting.
In an E2 reaction:
6. Which pair of electrons is acting in a nucleophilic fashion to cause the leaving group X-^ to be expelled from the molecule?
The bonding pair of electrons in the breaking C-H bond act as the nucleophile.
7. By considering the possible staggered conformations of the stereoisomer of 2-bromo,3-methyl pentane and the mechanism suggested below:
a) Explain why the major product of the E2 reaction is the trans isomer and the cis isomer is only a minor product.
The conformation where the pair of electrons in the C-H bond are directly behind the C-Br bond is shown on the next page. This conformation is most likely to react in an E2 mechanism and we see that the ethyl group and methyl group on the next carbon are on opposite sides and so are trans to each other in the alkene product.
continued on page 5
Discussion of answers 23DA Curly arrows and stereoselectivity in organic reactions
Base–
