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 0or 20carbon 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 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.

Short Answer

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New bonds are shown in bold

Step by step solution

01

Step-1. Explanation of part (a): 

The aromatic nitro group gets reduced to amino group in the presence of iron(III) catalyst and phenylsilane, ethanol. It is 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 carbon- all in a continuous sequence of reactions. The new bond forms which is attached to the ring containing alkene group.

Product formation using iron(III) catalyst, phenylsilane and ethanol

02

Step-2. Explanation of part (b)

The aromatic nitro group gets reduced to amino group in the presence of iron(III) catalyst and phenylsilane, ethanol. It is 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 carbon- all in a continuous sequence of reactions. The new bond forms which is attached to the ring containing alkene group

Product formation using iron(III) catalyst, phenylsilane and ethanol

03

Step-3. Explanation of part (c):

The aromatic nitro group gets reduced to amino group in the presence of iron(III) catalyst and phenylsilane, ethanol. It is 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 0carbon- all in a continuous sequence of reactions. The new bond forms which is attached to the ring containing alkene group.

04

Step-4. Expalantion of part (d);

Product formation using iron(III) catalyst, phenylsilane and ethanol

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Most popular questions from this chapter

Propose a mechanism for the sulfonation of pyridine, and point out why sulfonation occurs at 3-position.

Predict the products of the following reactions:

(a) excess  NH3  +  PhCH2CH2CH2Br

(b)1bromopentane(2)LiAlH4(3)H3O+(1)NaN3

(c)

(d) product  from  part  cheat

(e)

(f) product  from  part  e(3)heat(1)excessCH3I(2)Ag2O

(g)

(h)

(i)

(j) product  from  part  i(2)H3O+(1)LiAlH4

(k)

(l)

Macrolide antibiotics all have large rings (macrocycle) in which an ester makes the ring; a cyclic ester is termed a lactone. One example is erythromycin A, first isolated from soil bacteria in the 1950’s. Over time, some pathogenic bacteria have developed resistance to erythromycin by evolving an enzymatic mechanism to cleave the macrocycle at the ketone. To counter this resistance, chemists modified the erythromycin structure to replace the ketone with an amine that the bacteria could not detoxify. This modified antibiotic, azithromycin, trade name Zithromax®, is one of the most prescribed drugs in the world for respiratory infections.

(a) Identify the lactone group in each structure that merits the classification as macrolides.

(b) Two groups are circled. What type of functional group are they? Explain

(c) Identify the ketone in erythromycin targeted by bacteria as the site for detoxification.

(d) Identify the amine in azithromycin. What type of amine is it?

(e) From what you know about the reactivity of ketones and amines, why was an amine a good choice to be the “chemical opposite of a ketone”?

Propose a mechanism for the synthesis of methyl orange.

Propose a mechanism for nitration of pyridine at the 4-position, and show why this orientation is not observed.

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