13. Alcohols and Carbonyl Compounds

Propose a synthesis to accomplish the following transformation

Predict the product of the reaction

For each synthesis, start with bromocyclohexane and predict the products. Assume that an excess of each reactant is added so that all possible reactions that can happen will happen.

(a)

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⁺

Using the given starting material, any necessary inorganic reagents, and any carbon-containing compounds with no more than two carbons, indicate how each of the following compounds can be prepared:

b.

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)

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

(d)

Show how you might synthesize the following compounds starting with bromobenzene, and alkyl or alkenyl halides of four carbon atoms or fewer.

b. 5-methylhex-2-ene

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.

(a)

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

f.

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

b. (CH₃CH=CH)₂CuLi

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.]

(c)

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

(a)

What other product is formed in this reaction?