26. Amines

Predict the products of the following reactions:

(k)

Reductive amination of aldehydes and ketones is a versatile method for attaching alkyl groups to amines, but the alkyl group is restricted to a 1° or 2° carbon by this method. Prof. Phil Baran of Scripps Research Institute has reported (Science, 2015, 348 (6237), 886–891) a novel way to reduce an aromatic nitro group and add the resulting amine to an alkene so that the aromatic amine is bonded to a 3° carbon—all in a continuous sequence of reactions.

For example:

Predict the products using these starting materials, all of which are reported in this paper.

(c)

(d)

Predict the products of the following reactions:

(d)

The two most general amine syntheses are the reductive amination of carbonyl compounds and the reduction of amides. Show how these techniques can be used to accomplish the following syntheses.

(c) pyrrolidine → N-ethylpyrrolidine

Show how you can synthesize the following compounds starting with benzene, toluene, and alcohols containing no more than four carbon atoms as your organic starting materials. Assume that para is the major product (and separable from ortho) in ortho, para mixtures.

(b) N-methylbutan-1-amine

Show how you can synthesize the following compounds starting with benzene, toluene, and alcohols containing no more than four carbon atoms as your organic starting materials. Assume that para is the major product (and separable from ortho) in ortho, para mixtures.

(a) pentan-1-amine

Using any necessary reagents, show how you can accomplish the following multistep syntheses.

(c)

Propose a mechanism for the coupling of acetic acid and aniline using DCC as a coupling agent.