Final Examination

Chemistry 0310
November 23, 2020

Name: __________________________________

1. Provide examples that fit the following descriptions. Use structures! (20 points)
a) A reagent that undergoes [2+1] additions to alkenes.

b) A reagent or combination of reagents that undergoes syn-additions to alkenes.

c) A compound that would undergo SN1 reactions faster than SN2 reactions.

d) An organohalide that would be unlikely to undergo either an SN1 or an SN2 reaction.

e) An achiral disubstituted cyclohexane.

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2. The following questions pertain to the reaction shown below. Assume that it proceeds
exclusively through an SN2 pathway.
O Cl
NaCN
???
DMSO

a) Identify the stereocenters in the starting material. Prioritize the substituents according
to the Cahn-Ingold-Prelog protocol, and label the centers as R or S. (10 points)

b) Draw the two possible chair conformations of the starting material. Identify the more
stable conformation and calculate the energy difference. A-values for Cl and Me are 0.5
and 1.7 kcal/mol, respectively. (12 points)

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3. Assign reasonable structures for the following variables. Include stereochemistry
and/or alkene geometry where applicable. If no reaction is expected, write NR. Assume
that each reaction is subjected to an aqueous work-up and that the isolated products are
neutral compounds. (36 points)
a)
Hg(OAc)2
???
OH then NaBH4

b)
I2
MeOH ???

c)
O
???
H
O

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d) Note: this takes two steps.
O
??? S
Br

e)
???
OH

f)
Br
Br2
???
CH2Cl2
Br

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4. Agree or disagree with the following statements and explain your answers. (28 points)

a) Since m-CPBA reacts with E-2-butene to give a 1:1 mixture of stereoisomers, it will
necessarily react with the molecule shown below to give a 1:1 mixture of stereoisomers.
O
H
MeO O
H
O

b) RS–H bonds are approximately as strong as the Br–H bond. Therefore RS• groups will
show the approximately the same selectivity (with respect to forming primary, secondary,
or tertiary radicals) as Br• in hydrogen atom abstraction reactions.

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c) Nucleophilicity and basicity do not always correlate because nucleophilicity relates to
kinetics while basicity relates to thermodynamics.

d) Methyl iodide is a great nucleophile for additions into carbonyl groups that form
carbon–carbon bonds.

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5. Provide short answers to each of the following questions.

a) Use Newman projections to show why the energetic difference between the
diequatorial and diaxial conformations of trans-1,2-dimethylcyclohexane is less than the
sum of the two A-values by 0.6 kcal/mol. No Newman projection = no points. (8 points)

b) Why does the reaction shown below yield a product with no optical rotation? (6
points)

H2, Pd/C Product that does not

rotate plane polarized
O light

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6. Provide a stepwise mechanism for the following reaction using arrows. Explain
regiochemistry when necessary. If you can't do the whole thing then show as much as
you know. Note that HO• is not something that can be added from a bottle, but is
generated through an unseen reaction. Just assume that is can be formed readily. (12
points)

HBr
HO• Br

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7. Propose a synthesis of the following molecule from starting materials that contain four
or fewer carbons. (12 points)

Cl

OH

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Break time

In the old movie "Back to School" Rodney Dangerfield was forced to endure an extensive
oral exam. His poetry professor, played by Sally Kellerman, asked him to recite a poem.
The exchange went something like:
Sally:
Do you remember the Dylan Thomas poem "Do Not Go Gently into that Good Night"?
Rodney: (tentatively at first, then stronger)
Do not go gentle into that good night,
Old age should burn and rave at close of day;
Rage, rage against the dying of the light.
Though wise men know at their end dark is right,
Because their words had forked no lightning they
Do not go gentle into that good night.
Good men, the last wave by, crying how bright
Their frail deeds might have danced in a green bay,
Rage, rage against the dying of the light.
Wild men who caught and sang the sun in flight,
And learned, too late, they grieved it on its way,
Do not go gentle into that good night.
Grave men, near death, who see with blinding sight
Blind eyes could blaze like meteors and be gay,
Rage, rage against the dying of the light.
And you, my father, there on that sad height,
Curse, bless, me now with your fierce tears, I pray.
Do not go gentle into that good night.
Rage, rage against the dying of the light.
Sally:
Do you know what this means?
Rodney:
It means I don't take s*** from anyone. I'm going to pass this exam!

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8. Hydroboration of terminal alkynes followed by oxidative work up yields aldehydes
rather than ketones. This was determined by spectroscopic analysis of the products and
comparing the results to all expected outcomes. Draw the 1H NMR spectra of both
isomeric possible hydration products of 1-butyne hydroboration/oxidation. Include
chemical shifts, multiplicities, and peak ratios (integrations). If you don't think you can
draw the spectra clearly then put the values into a table. Note that this is a spectroscopy
problem rather than an alkyne problem – you do not need to know how this happens. (12
points)

“H2O” O H
or
O

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9. Identify the thermodynamic driving force for the following reactions. (18 points)

a)
O OH
H

b)
O + I O + I–

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c)
+ Li + H
H Li

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10. What additional information do you need to answer the following questions? (12
points)

a) Do alcohols react with SOCl2 to form alkyl chlorides through an SN1 or an SN2
mechanism?

b) Will the number of 13C NMR signals match the number of carbons in the molecule?

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11. Mini-synthesis. Achieve the following transformation in two steps. If you can't do
that then do what you can. (8 points)

OH

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12. Two approaches to a migration-based approach to the formation of a tertiary alcohol
are shown below. Each has at least one disadvantage based on the principles of green
chemistry. Identify the disadvantage for each of the reactions. (6 points)

H2SO4 HO
Δ
OH

AgNO3, H2O
HO + AgNO3 + HBr
room temperature
Br

And that's all there is. Have a great break!

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