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Carbohydrates - Cyclic structures and anomers

Explore how chains of carbon atoms form carbohydrates, discover the magic of intramolecular reactions, and learn about the formation of stable rings. Uncover the secrets of pyranoses and furanoses, and get to grips with the Haworth diagram and chair confirmation. Created by Ryan Scott Patton.

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Video transcript

- [Voiceover] All righty, so we've been speaking so far about carbohydrates as chains of carbon atoms and these are chains of carbon atoms that feature an aldehyde or a ketone functional group and that falls into this general kind of one to two to one ratio of carbon, hydrogen and oxygen and of course I'll keep using glucose as an example. Now I've also used the term polyhydroxylated to refer to the numerous hydroxyl groups that are in these carbohydrates and really I bring all of these verbiage back up to hopefully spark your ability to see that carbohydrates have all the makings of an internal or intramolecular, I guess reaction between the carbinol carbon right here and one of the hydroxyl groups because essentially what we have is carbinol and alcohol chemical reaction just waiting to happen. What happens when an alcohol nucleophile attacks an aldehyde or a ketone? Well if there's an excess of alcohol, we end up with a product that is either an acetal or a ketal but what happens if there's only one nucleophilic attacked by an alcohol. If we just have one alcohol and that's gonna be the case in the ring closing intramolecular reaction we have going on here. Well in that case we end up with a hemiacetal or a hemiketal, and really that terminology is just a review of acetal and ketal chemical reactions that would fall under I guess if you're looking in an organic chemistry book aldehyde or ketone reactions probably in the carbonyl section. Let's show how this process is happening in the context of our glucose over here. First I'm gonna highlight the particular hydroxyl oxygen that's gonna act as the nucleophile, so we'll make that pink. After being deprotonated, so after losing this proton, this oxygen is gonna have an extra set of electrons right here and those electrons are gonna target that carbonyl carbon. I'll draw the carbonyl carbon in green and remember that the carbonyl carbon has a partial positive charge on it, it has a partial positive charge because a lot of the electron density in this double bond is being hugged by this oxygen. The oxygen has a partially negative charge and that carbonyl carbon is partially positive and that makes it a perfect target for the nucleophile that's been created in the deprotonation process of this oxygen. After the oxygen's electrons attack this carbonyl carbon, what's gonna happen is the electrons from the settle bond are gonna kick back up to the oxygen up here and eventually they're gonna attract another proton and will form another hydroxyl group out of some of the electrons from that bond. You might be asking and it's a perfectly valid question why is this particular oxygen the one that I've highlighted that's acting as the nucleophile. You're gonna see as soon as I get the product drawn that we formed a six member ring. It really has a lot to do with product stability and if you remember the basis for the formation of the ring in the first place was the increase stability over the straight carbon chain. It makes sense that we're gonna form the most stable ring that we can. When we end up with the six membered carbohydrate ring such as the case with glucose here, we call the product a pyranose, the ose again as the suffix for sugar and the pyr part to indicate that this ring is a sugar with six carbons and then if the carbohydrate ring is a five carbon ring, we call a furanose which is a bit easier for me to remember because furanose and five both start with a letter F. That's kind of the memory jogger for me and maybe a good example for that would be ribose with its five carbon chain but I'll kinda stop there because almost every ring forming carbohydrate that I can think of with biological implications at least forms, either a five or a six membered rings, so pyranoses and furanoses. Just by convention, you can see that I've placed the O in this corner up here and that places the formally carbonyl carbon down here, right below it and it's actually no longer the carbonyl carbon but it's still significant because it's the only carbon here that is bonded to two oxygen atoms, the highlighted oxygen and it's bonded to another hydroxyl here as well. I'll keep a distinguishing color and we also distinguish it's name now as the anomeric carbon. That's the anomeric carbon and then we can go ahead and fill in the rest of the substituents in the diagram, so a hydroxyl group and another and another. We call this diagram a Haworth diagram. The Haworth diagram doesn't show as the actual configuration of the ring because in reality six membered rings are gonna show up in a more stable chair shape but it is beneficial in telling us which substituents are above or below the ring. To keep this convention straight in my mind, I remember the phrase downright up lefting. Kind of a play on I guess the phrase that's downright uplifting but downright up lefting because as I fill in the substituents, those on the right side of the Fischer diagram will point down and those on the left side of the Fischer diagram are gonna point up. We can actually see that that one's up and we'll make sure that this number's off right. This one's up as well and maybe we'll name this or maybe we'll start numbering with one, two, three, four, five, six and we can do that over here. This would be one, two, three, four, five, six. Our three carbon in the Haworth diagram is pointed up and our three carbon on the Fischer diagram has its substituent on the left, so downright, up, left. As we get to the last carbon group which forms this tail down here. I remember that if it's a d sugar, that group is gonna point up in the Haworth projection. This is a d sugar and you can see in the Haworth projection that this last carbon points up as well and really this is gonna be the case for a lot of sugar chemistry that you deal with because again we're into matically programmed to digest d sugars so we often end up with this last group pointing up. Now the last thing I wanna show you is the chair confirmation and that's because this is the kind of diagram that's gonna give us a sense for that actual configuration of a d glucose but it really does just follow through with the Haworth projection as far as the substituents being above or below the ring. Let me just keep filling in the substituents here and I'll number them off. Again just so you can see that there's some consistency here. We've got one, two, three, four, five, six and again this three carbon right here is the only one with the hydroxyl group pointing up and I guess I better change the color of our one carbon to keep that consistent as well. Now I didn't indicate the position of the anomeric carbons hydroxyl group yet because I think it makes more sense to show it in this diagram. Remember that the original nucleophilic attack by the oxygen way back over here. That could have created two different products, one with an r configuration about the anomeric carbon and the other with a s configuration. That last hydroxyl group can actually be in two different positions. On one hand the hydroxyl group would be cis to the last carbon in the equatorial position. It would cis to this last carbon over here and it's in the equatorial position and we call this the beta anomer then on the other hand I guess it could be trans to that last carbon group which would place it in that axial position down here. I guess it could be down here in the axial position and we call it the alpha anomer, when the hydroxyl group is in the axial and I can remember that a little bit easier. Alpha for the axial position of that substituent. I guess I've also heard that fishes are down in the sea and birds are up in the air so if that helps you keep them straight, you might be able to use that also. Now you've got to remember that what caused this ring to close in the first place was some amount of acid or base and the amount of acid and base and water is actually capable of doing that because that's what facilitated this ring closing process in the first place. In water, the ring can actually open and close spontaneously. When it opens up, the c1 and c2 bond right here can actually rotate and when it closes again, you can form either the alpha or the beta product. This thing is constantly opening and closing to form the two different products and we call that process where it opens and rotates and closes again, mutarotation. This thing is mutarotating in the water at all times. Mutarotation and the outcome is that we end up with both configurations, the beta and the alpha and the equilibrium concentration. For glucose, that's gonna be about 36% alpha and about 64% beta. The reason that the alpha configuration is less favored in equilibrium for glucose is because the transpositioning of the hydroxyl group creates some steric hindrance but this is pretty individualized for different sugars. I guess the most general rule I suppose that you could apply to all cyclic sugars would be to say that the beta anomer, again anomer, that the beta anomer is the one with the anomeric oxygen in the cis position with respect to the last carbon.