13. Alcohols and Carbonyl Compounds

Predict the product of the reaction

Predict the product of the reaction

Predict the product of the reaction

Predict the product of the reaction

Propose a synthesis to accomplish the following transformation

Propose a synthesis to accomplish the following transformation

Predict the product of the reaction

Predict the product of the diorganocuprate cross-coupling reactions shown.

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Suggest a synthesis of the following molecule starting with the reagents shown, using cuprate cross-coupling as the key step. [You will need a reaction from Chapter 13 to complete this synthesis.]

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(•••) Suggest a synthetic scheme, involving a protecting group, to generate the molecule shown starting with the molecule at the left.

(d) <IMAGE>

(•••) Suggest a synthetic scheme, involving a protecting group, to generate the molecule shown starting with the molecule at the left.

(b) <IMAGE>

Predict the product of the following reactions.

(b) <IMAGE>

Suggest a series of steps involving a cuprate reagent that would convert the reactant on the left to the product on the right. The ideal number of steps is shown.

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Suggest a reagent and a reactant that could be used to form the following molecules by conjugate addition of a cuprate. There can be multiple possibilities.

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To this point, we have seen four reactions that can be done by Gilman reagents. What are they? What do they have in common?

(••) Phenol oxidation can be coupled with other reactions to form new C―C bonds using reactions studied previously. Predict the product of the following series of reactions.

(b) <IMAGE>

What are the products of the following reactions?

b. <IMAGE>

What are the products of the following reactions? Show all stereoisomers that are formed.

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b. <IMAGE>

What product is formed when 3-methyl-2-cyclohexenone reacts with each of the following reagents?

a. CH3MgBr followed by H3O+

b. (CH3CH2)2CuLi followed by H3O+

The Reformatsky reaction is an addition reaction in which an organozinc reagent is used instead of a Grignard reagent to add to the carbonyl group of

an aldehyde or a ketone. Because the organozinc reagent is less reactive than a Grignard reagent, a nucleophilic addition to the ester group does not occur.

The organozinc reagent is prepared by treating an a-bromo ester with zinc.

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Describe how each of the following compounds can be prepared, using a Reformatsky reaction:

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Using bromocyclohexane as a starting material, how could you synthesize the following compounds?

a. <IMAGE>

What alcohols are formed from the reaction of ethylene oxide with the following organocuprates followed by the addition of acid?

b. (CH3CH=CH)2CuLi

Show how you would synthesize the following compound from alkyl halides, vinyl halides, and aryl halides containing no more than six carbon atoms.

(d) cyclopentyl propyl ketone

Show how you would accomplish the following synthetic

conversions by adding an organolithium reagent to an acid.

(c) pentanoic acid → heptan-3-one

(d) phenylacetic acid → 3,3-dimethyl-1-phenylbutan-2-one

Predict the products of the following reactions: (c) <IMAGE of reaction> (d) <IMAGE of reaction>

Show how you would accomplish the following synthetic

conversions by adding an organolithium reagent to an acid.

(d) phenylacetic acid → 3,3-dimethyl-1-phenylbutan-2-one

Propose structures for intermediates and products (A) through (K)

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Devise a synthesis for each compound, starting with methylenecyclohexane and any other reagents you need.

(f) 1-(phenylmethyl)cyclohexanol

Show how you would accomplish the following synthetic

conversions by adding an organolithium reagent to an acid.

(a) <IMAGE of reaction>

Show how you would accomplish the following synthetic

conversions by adding an organolithium reagent to an acid.

(b) <IMAGE of reaction>

Draw the organic products you would expect to isolate from the following reactions (after hydrolysis).

(p) <IMAGE>

Predict the major products of the following reactions.

(g) <IMAGE of reaction>

Draw the organic products you would expect to isolate from the following reactions (after hydrolysis).

(a) <IMAGE>

(b) <IMAGE>

Predict the products of the following reactions.

(d) <IMAGE>

(e) <IMAGE>

Suggest the most appropriate method for each of the following 

laboratory syntheses. In each case, suggest both 

a chromium reagent and a chromium-free reagent.

(d) cyclopentanol → 1-ethylcyclopentanol (two steps)

(e) cyclopentylmethanol → 1-cyclopentylpropan-1-ol (two steps)

Develop syntheses for the following compounds. As starting materials, you may use cyclopentanol, alcohols containing no more than four carbon atoms, and any common reagents and solvents.

(d) <IMAGE>

Show how you would synthesize the following compounds from any starting materials containing no more than six carbon atoms.

(b) <IMAGE>

Develop syntheses for the following compounds. As starting materials, you may use cyclopentanol, alcohols containing no more than four carbon atoms, and any common reagents and solvents.

(e) <IMAGE>

Develop syntheses for the following compounds. As starting materials, you may use cyclopentanol, alcohols containing no more than four carbon atoms, and any common reagents and solvents.

(f) <IMAGE>

Muscalure is the sex attractant of the common housefly. Flies are lured to traps filled with bait that contain muscalure and an insecticide. Eating the bait is fatal. How could you synthesize muscalure using 1-bromopentane as one of the starting materials?

A variety of organometallics, which as strong nucleophiles can react with epoxides, are introduced in Chapter 16. Predict the product of these reactions. [Hint: Assume the carbon–metal bond in each is ionic, with the carbon possessing the negative charge.]

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Give the structures of intermediates A through H in the following synthesis of trans-1-cyclohexyl-2-methoxycyclohexane.

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For each of the following carbonyl addition reactions, would you expect a racemic mixture or a mixture enriched in one stereoisomer? In each case, draw both possible stereoisomeric products.

(a) <IMAGE>

Predict the product of the following aldehyde and ketone addition reactions.

(a) <IMAGE>

Predict the product of the following aldehyde and ketone addition reactions.

(c) <IMAGE>

b. What other product is formed in this reaction?

Using the given starting material, any necessary inorganic reagents and catalysts, and any carbon-containing compounds with no more than three carbons,

indicate how each of the following compounds can be prepared:

f. <IMAGE>

What bromo-substituted compound would be required to react with (CH2=CH)2CuLi in order to form

each of the following compounds?

b. <IMAGE>

What alkyl halide reacts with lithium divinylcuprate 3(CH2=CH)2CuLi4 for the synthesis of each of the following compounds?

a. <IMAGE>

b. <IMAGE>

Design a synthesis for each of the following, using an intramolecular reaction:

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a. Metathesis of which of the following sets of alkenes leads to the highest yield of a single alkene?

1. 1-butene and 1-pentene 

2. 2-butene and 3-hexene 

3. 2-butene and 1-pentene