13. Alcohols and Carbonyl Compounds

Suggest a synthesis of the following molecule starting with the reagents shown, using cuprate cross-coupling as the key step.

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

(d)

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

(b)

Predict the product of the following reactions.

(b)

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.

(c)

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.

(c)

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)

What are the products of the following reactions?

a.

b.

What are the products of the following reactions?

b.

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

a.

b.

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 α-bromo ester with zinc.

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

a.

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

a.

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

b. (CH₃CH=CH)₂CuLi