10. Addition Reactions

Predict the product of each of the following alcohol synthesis reactions.

(a)

Predict the product(s) that would result when the alkenes shown here are allowed to react under the following conditions: (v) 1. Hg(OAc)₂ , H₂O 2. NaBH₄

(g)

Assessment 8.74 revealed that oxymercuration could be used to make cyclic esters. Suggest a likely mechanism for this transformation.

Provide an arrow-pushing mechanism, accounting also for the stereochemical outcome, of the first step (oxymercuration) of the three reactions in Figure 8.63.

In light of your answer to Assessment 8.73, predict the product of the following oxymercuration–reduction reactions, each of which results in a single product. [Don't worry about the absolute stereochemistry, though these reactions are also stereoselective.]

(b) This reaction sequence was used in the synthesis of (+) -lineatin, a monoterpene aggregation pheromone from the female ambrosia beetle Trypodendron lineatum (Org. Lett. 2004, 6, 1449–1452).

Show how you would accomplish the following transformations.

(a)

In light of your answer to Assessment 8.73, predict the product of the following oxymercuration–reduction reactions, each of which results in a single product. [Don't worry about the absolute stereochemistry, though these reactions are also stereoselective.]

(c) Oxymercuration–reduction was used in the stereoselective synthesis of the macrolactone core of neopeltolide, a marine macrolide isolated from a Caribbean sponge that has potent anticancer activity (Org. Lett. 2012, 14, 2346–2349).

The first step of oxymercuration–reduction is stereospecific, and yet this fact wasn't emphasized in that discussion. Show the stereospecificity of the first step for the following alkene and then explain why the stereospecificity becomes unimportant after the second step.

Predict the product(s) that would result when the following molecules are allowed to react under the following conditions: (ii) 1. Hg(OAc)₂ 2. NaBH₄.If there is no reaction, write 'no reaction.'

(a)

Predict the products you would get when the following alkenes react under the following conditions: (ii) 1. Hg(OAc)₂ , H₂O , 2. NaBH₄

(a)

Predict the product of the following reaction.

Predict the product of the following aldehyde/ketone syntheses.

(d)

Predict the major products of the following reactions.

c. 4−chlorocycloheptene + Hg(OAc)₂ in CH₃OH

d. the product from part (c), treated with NaBH₄

At the beginning of Chapter 9, we stated that after finishing Chapters 8 and 9, we would have the ability to make a large variety of functional groups using related reactions. Show the reagent(s) necessary to convert 1-isobutylcyclohexene into the following molecules.

(h)

Which is more stable, a carbocation or a mercurinium ion? How do you know?