Emil Fischer synthesized L-gulose, an unusual aldohexose that reduces to give D-glucitol. Suggest a structure for this L sugar, and show how L-gulose gives the same alditol as D-glucose. (Hint: D-Glucitol has -CH2OHgroups at both ends. Either of these primary alcohol groups might have come from reduction of an aldehyde.)

Short Answer

Expert verified

Aldoses and ketoses can be reduced to their corresponding polyalcohols, known as sugar alcohols or alditols by using the reagents such as sodium borohydride (NaBH4) or by catalytic hydrogenation using a nickel (Ni) catalyst.

Step by step solution

01

Alditols

Aldoses and ketoses can be reduced to their corresponding polyalcohols, known as sugar alcohols or alditols by using the reagents such as sodium borohydride (NaBH4) or by catalytic hydrogenation using a nickel (Ni) catalyst.

02

Naming of alditols

Alditols are named by adding a suffix -itol to the root name of the sugar.

03

D- and L- series of sugars

For D - series of sugars, the OH group of the bottom asymmetric carbon atom is on the right side in the Fischer projection. Again, for L - series of sugars, the OH group of the bottom asymmetric carbon atom is on the left side in the Fischer projection. D - and L - refers to the absolute configuration around the asymmetric carbon atom while (+) and (-) refers to the direction of rotation of the plane polarised light.

04

Synthesis

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Most popular questions from this chapter

When the gum of the shrub Sterculia setigera is subjected to acidic hydrolysis, one of the water-soluble components of the hydrolysate is found to be tagatose. The following information is known about tagatose:

(1) Molecular formula C6H12O6

(2) Undergoes mutarotation.

(3) Does not react with bromine water.

(4) Reduces Tollens reagent to give d-galactonic acid and d-talonic acid.

(5) Methylation of tagatose (using excess CH3 I and Ag2O) followed by acidic hydrolysis gives 1,3,4,5-tetra-O-methyltagatose.

(a) Draw a Fischer projection structure for the open-chain form of tagatose.

(b) Draw the most stable conformation of the most stable cyclic hemiacetal form of tagatose.

Cytosine, uracil and guanine have tautomeric forms with aromatic hydroxyl groups. Draw these tautomeric forms.

Fructose is found in many fruits. From memory, draw fructose in

  1. the Fischer projection of the open chain.
  2. The most stable chair conformation of the most stable pyranose anomer.
  3. The Haworth projection of the most stable pyranose anomer

Question: Propose a mechanism for methylation of any one of the hydroxy groups of methyl-α-D-glucopyranoside,using and dimethyl sulfate.

H. G. Khorana won the Nobel Prize in Medicine in 1968 for developing the synthesis of DNA and RNA and for helping to unravel the genetic code. Part of the chemistry he developed was the use of selective protecting groups for the 5′ OH group of nucleosides.

The trityl ether derivative of just the 5′ OH group is obtained by reaction of the nucleoside with trityl chloride, MMT chloride, or DMT chloride and a base like Et3N. The trityl ether derivative can be removed in dilute aqueous acid. DMT derivatives hydrolyze fastest, followed by MMT derivatives, and trityl derivatives slowest.

(a) Draw the product with the trityl derivative on the 5′ oxygen.

(b) Explain why the trityl derivative is selective for the 5′ OH group. Why doesn’t it react at 2′ or 3′? (c) Why is the DMT group easiest to remove under dilute acid conditions? Why does the solution instantly turn orange when acid is added to a DMT derivative?

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