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{{Short description|Molecules which are non-mirror image, non-identical stereoisomers}}
'''Diastereomers''' (or '''diastereoisomers''') are [[stereoisomer]]s that are not [[enantiomer]]s (mirror images of each other). Diastereomers can have different physical properties and different reactivity. In another definition diastereomers are pairs of isomers that have opposite configurations at one or more of the chiral centers but are not mirror images of each other <ref>Garrett, Grisham "Biochemistry" 2nd ed., 1999, p. 213</ref>.
{{more citations needed|date=September 2021}}
{| align="right" class="wikitable"
|-
!colspan="2"|Diastereomers that are also epimers
|-
|bgcolor="#FFFFFF"| [[File:D-threose.svg|150px]]
|bgcolor="#FFFFFF"| [[File:D-erythrose.svg|150px]]
|-
|bgcolor="#FFFFFF"| [[File:DThreose Fischer.svg|166px]]
|bgcolor="#FFFFFF"| [[File:DErythrose Fischer.svg|144px]]
|-
| [[Threose|<small>D</small>-threose]]
| [[Erythrose|<small>D</small>-erythrose]]
|}


In [[stereochemistry]], '''diastereomers''' (sometimes called '''diastereoisomers''') are a type of [[stereoisomer]].<ref>IUPAC "Gold Book" [http://goldbook.iupac.org/D01679.html ''diastereoisomerism''] &nbsp;{{doi|10.1351/goldbook.D01679}}</ref> Diastereomers are defined as non-mirror image, non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent (related) [[stereocenter]]s and are not mirror images of each other.<ref>{{citation | last1=Garrett | first1=R.H. | last2=Grisham | first2=C.M. | title=Biochemistry 3rd ed.| year=2005| page=205 | isbn=0-534-41020-0| publisher=Thomson | place=Belmont CA}}.</ref>
In ''simple terms'' two stereoisomers are said to be diastereoisomers if they are not mirror images of each other and '''one or more''' [[stereogenic]] centres differ between the two stereoisomers. According to this same definition, [[geometric isomerism]] is a form of diastereomerism.
When two diastereoisomers differ from each other at only one stereocenter, they are [[epimer]]s. Each stereocenter gives rise to two different configurations and thus typically increases the number of stereoisomers by a factor of two.


Diastereomers differ from [[enantiomer]]s in that the latter are pairs of stereoisomers that differ in all stereocenters and are therefore mirror images of one another.<ref>[[IUPAC]] "Gold Book" [http://goldbook.iupac.org/E02069.html ''enantiomer''] &nbsp;{{doi|10.1351/goldbook.E02069}}</ref>
If a [[molecule]] contains a single asymmetric [[carbon]] [[atom]] or [[stereocenter]], it will have two mirror image forms. If a molecule contains two asymmetric carbons, there are up to 4 possible configurations, and they cannot all be mirror images of each other. The possibilities continue to multiply as there are more asymmetric centers in a molecule.
Enantiomers of a compound with more than one stereocenter are also diastereomers of the other stereoisomers of that compound that are not their mirror image (that is, excluding the opposing enantiomer).
Diastereomers have different physical properties (unlike most aspects of enantiomers) and often different [[chemical reactivity]].


Diastereomers differ not only in physical properties but also in chemical reactivity — how a compound reacts with others. Glucose and [[galactose]], for instance, are diastereomers. Even though they share the same molar weight, glucose is more stable than galactose. This difference in stability causes galactose to be absorbed slightly faster than glucose in human body.<ref>{{Cite journal |last1=McCance |first1=Robert Alexander |last2=Madders |first2=Kate |date=1930 |title=The comparative rates of absorption of sugars from the human intestine |journal=Biochemical Journal |volume=24 |issue=3 |pages=795–804 |doi=10.1042/bj0240795 |issn=0264-6021 |pmc=1254520 |pmid=16744419}}</ref><ref>{{Cite journal |last1=Chao |first1=Hsi-Chun |last2=McLuckey |first2=Scott A. |date=2020-10-06 |title=Differentiation and Quantification of Diastereomeric Pairs of Glycosphingolipids using Gas-phase Ion Chemistry |journal=Analytical Chemistry |volume=92 |issue=19 |pages=13387–13395 |doi=10.1021/acs.analchem.0c02755 |issn=0003-2700 |pmc=7544660 |pmid=32883073}}</ref>
[[Tartaric acid]] contains two asymmetric centers, but two of the "isomers" are equivalent and are called a [[meso compound]]. This configuration is not [[optical activity|optically active]], while the remaining two isomers are <small>D</small>- and <small>L</small>- mirror images, ''i.e.'' enantiomers. The meso form is a diastereomer of the other forms.

'''Diastereoselectivity''' is the preference for the formation of one or more than one diastereomer over the other in an [[organic reaction]]. In general, [[stereoselectivity]] is attributed to torsional and steric interactions in the [[stereocenter]] resulting from [[electrophile]]s approaching the stereocenter in reaction.<ref>{{Cite journal |last1=Lavinda |first1=Olga |last2=Witt |first2=Collin H. |last3=Woerpel |first3=K. A. |date=2022-03-28 |title=Origin of High Diastereoselectivity in Reactions of Seven-Membered-Ring Enolates |journal=Angewandte Chemie International Edition in English |volume=61 |issue=14 |pages=e202114183 |doi=10.1002/anie.202114183 |issn=1521-3773 |pmc=8940697 |pmid=35076978}}</ref>
{| cellpadding="5" cellspacing="0"

==Syn / anti==
When the single bond between the two centres is free to rotate, cis/trans descriptors become invalid. Two widely accepted prefixes used to distinguish diastereomers on sp³-hybridised bonds in an open-chain molecule are '''syn''' and '''anti'''. Masamune proposed the descriptors which work even if the groups are not attached to adjacent carbon atoms. It also works regardless of [[Cahn-Ingold-Prelog priority rules|CIP]] priorities. Syn describes groups on the same face while anti describes groups on opposite faces. The concept applies only to the Zigzag projection. The descriptors only describe relative stereochemistry rather than absolute stereochemistry.
All isomers are same.

==Erythro / threo==
Two older prefixes still commonly used to distinguish diastereomers are '''threo''' and '''erythro'''. In the case of saccharides, when drawn in the [[Fischer projection]] the erythro isomer has two identical substituents on the same side and the threo isomer has them on opposite sides.<ref>''Modern physical organic chemistry'' Eric V. Anslyn, Dennis A. Dougherty 2006</ref> When drawn as a zig-zag chain, the erythro isomer has two identical substituents on different sides of the plane (anti). The names are derived from the diastereomeric four-carbon [[aldose]]s [[erythrose]] and [[threose]]. These prefixes are not recommended for use outside of the realm of saccharides because their definitions can lead to conflicting interpretations.<ref>{{GoldBookRef|title=erythro, threo|file=E02212}}</ref>

Another threo compound is [[threonine]], one of the essential amino acids. The ''erythro'' diastereomer of it is [[allothreonine]].

{| class="wikitable centered" style="text-align:center"<br>
|-
|-
| [[File:L-Threonin - L-Threonine.svg|180px]]&nbsp;[[File:D-Threonine.svg|180px]]<br>
| align="center" width="150" style="border-right:1px dashed black;" |
[[Image:L-tartaric acid.png]]
| align="center" width="150" style="border-right:1px solid black;" | [[Image:D-tartaric acid.png]]
| align="center" width="270" | [[Image:DL-tartaric acid.png]]
|-
|-
| <small>L</small>-Threonine (2''S'',3''R'') and <small>D</small>-Threonine (2''R'',3''S'')<br>
| align="center" valign="bottom" style="border-right:1px dashed black;" |
|-
(natural) tartaric acid<br><small>L</small>-(+)-tartaric acid<br>dextrotartaric acid
| [[File:L-allo-Threonine.svg|180px]]&nbsp;[[File:D-allo-Threonine.svg|180px]]<br>
| align="center" valign="bottom" style="border-right:1px solid black;" |
|-
<small>D</small>-(-)-tartaric acid<br>levotartaric acid<br>
| <small>L</small>-Allothreonine (2''S'',3''S'') and <small>D</small>-[[Allothreonine]] (2''R'',3''R'')
| align="center" valign="middle" |
mesotartaric acid
|-
|-
| align="center" colspan="2" valign="bottom" style="border-right:1px solid black;" |
(1:1)<br><small>DL</small>-tartaric acid<br>"racemic acid"
|
|}
|}


== Multiple stereocenters ==
The families of 4, 5 and 6 carbon [[carbohydrate]]s contain many diastereomers because of the large numbers of asymmetric centres in these molecules.
Two common prefixes used to distinguish diastereomers are '''threo''' and '''erythro'''. When drawn in the [[Fischer projection]] the erythro isomer has two identical substituents on the same side and the threo isomer has them on opposite sites.
[[Cis-trans isomerism]] and [[conformational isomerism]] are also forms of diastereomerism.


If a molecule contains two asymmetric centers, there are up to four possible configurations, and they cannot all be non-superposable mirror images of each other. The possibilities for different isomers continue to multiply as more stereocenters are added to a molecule. In general, the number of stereoisomers of a molecule can be determined by calculating 2<sup>''n''</sup>, where ''n''&nbsp;=&nbsp;the number of [[Chirality (chemistry)|chiral]] centers in the molecule. This holds true except in cases where the molecule has [[meso compounds|meso]] forms. These [[meso compound]]s are molecules that contain [[stereocenter]]s, but possess an internal plane of symmetry allowing it to be superposed on its mirror image. These equivalent configurations cannot be considered diastereomers.<ref>{{Cite journal |last1=Merad |first1=Jérémy |last2=Candy |first2=Mathieu |last3=Pons |first3=Jean-Marc |last4=Bressy |first4=Cyril |date=May 2017 |title=Catalytic Enantioselective Desymmetrization of Meso Compounds in Total Synthesis of Natural Products: Towards an Economy of Chiral Reagents |url=http://www.thieme-connect.de/DOI/DOI?10.1055/s-0036-1589493 |journal=Synthesis |language=en |volume=49 |issue=9 |pages=1938–1954 |doi=10.1055/s-0036-1589493 |s2cid=99010495 |issn=0039-7881}}</ref>
'''Diastereoselectivity''' is the preference for the formation of one or more than one diastereomer over the other in an [[organic reaction]].

For ''n'' = 3, there are eight stereoisomers. Among them, there are four pairs of enantiomers: R,R,R and S,S,S; R,R,S and S,S,R; R,S,S and S,R,R; and R,S,R and S,R,S. There are many more pairs of diastereomers, because each of these configurations is a diastereomer with respect to every other configuration excluding its own enantiomer (for example, R,R,R is a diastereomer of R,R,S; R,S,R; and R,S,S). For ''n'' = 4, there are sixteen stereoisomers, or eight pairs of enantiomers. The four enantiomeric pairs of [[pentose|aldopentoses]] and the eight enantiomeric pairs of [[hexose|aldohexoses]] (subsets of the five- and six-carbon sugars) are examples of sets of compounds that differ in this way.

== Diastereomerism at a double bond ==
Double bond isomers are always considered diastereomers, not enantiomers. Diastereomerism can also occur at a [[double bond]], where the [[Cis–trans isomerism|''cis'' vs ''trans'' relative positions]] of [[substituents]] give two non-superposable isomers. Many [[Conformational isomerism|conformational isomers]] are diastereomers as well.

In the case of diastereomerism occurring at a double bond, [[E–Z notation|E-Z]], or entgegen and zusammen (German), is used in notating [[nomenclature]] of [[alkene]]s.<ref>{{Cite book |last=Brown |first=William |title=Organic Chemistry |publisher=Cengage Learning |year=2018 |isbn=9781305580350 |edition=8th |location=United States |pages=138–142 |language=English}}</ref>


==Applications==
==Applications==
As stated, two enantiomers will have identical physical properties, while diastereomers will not. This knowledge is harnessed in [[chiral synthesis]] to separate a mixture of enantiomers. This is the principle behind [[chiral resolution]]. After preparing the diastereomers, they are separated by [[chromatography]] or [[recrystallization]].
As stated previously, two diastereomers will not have identical chemical properties. This knowledge is harnessed in [[chiral synthesis]] to separate a mixture of enantiomers. This is the principle behind [[chiral resolution]]. After preparing the diastereomers, they are separated by [[chromatography]] or [[Recrystallization (chemistry)|recrystallization]]. Note also the example of the [[stereochemistry of ketonization of enols and enolates]].


==See also==
==See also==
*[[Cahn–Ingold–Prelog priority rules]] for nomenclature.
* [[Stereochemistry]]


==References==
==References==
{{Reflist}}
<div class="references-small"><references/><div>


{{Chiral synthesis}}
[[Category:Stereochemistry]]


[[Category:Stereochemistry]]
[[ar:مقابل غير ضوئي]]
[[Category:Isomerism]]
[[de:Diastereomer]]
[[nl:Diastereomeer]]
[[ja:ジアステレオマー]]
[[pl:Diastereoizomer]]
[[fi:Diastereomeeri]]

Latest revision as of 10:27, 24 July 2024

Diastereomers that are also epimers
D-threose D-erythrose

In stereochemistry, diastereomers (sometimes called diastereoisomers) are a type of stereoisomer.[1] Diastereomers are defined as non-mirror image, non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent (related) stereocenters and are not mirror images of each other.[2] When two diastereoisomers differ from each other at only one stereocenter, they are epimers. Each stereocenter gives rise to two different configurations and thus typically increases the number of stereoisomers by a factor of two.

Diastereomers differ from enantiomers in that the latter are pairs of stereoisomers that differ in all stereocenters and are therefore mirror images of one another.[3] Enantiomers of a compound with more than one stereocenter are also diastereomers of the other stereoisomers of that compound that are not their mirror image (that is, excluding the opposing enantiomer). Diastereomers have different physical properties (unlike most aspects of enantiomers) and often different chemical reactivity.

Diastereomers differ not only in physical properties but also in chemical reactivity — how a compound reacts with others. Glucose and galactose, for instance, are diastereomers. Even though they share the same molar weight, glucose is more stable than galactose. This difference in stability causes galactose to be absorbed slightly faster than glucose in human body.[4][5]

Diastereoselectivity is the preference for the formation of one or more than one diastereomer over the other in an organic reaction. In general, stereoselectivity is attributed to torsional and steric interactions in the stereocenter resulting from electrophiles approaching the stereocenter in reaction.[6]

Syn / anti

[edit]

When the single bond between the two centres is free to rotate, cis/trans descriptors become invalid. Two widely accepted prefixes used to distinguish diastereomers on sp³-hybridised bonds in an open-chain molecule are syn and anti. Masamune proposed the descriptors which work even if the groups are not attached to adjacent carbon atoms. It also works regardless of CIP priorities. Syn describes groups on the same face while anti describes groups on opposite faces. The concept applies only to the Zigzag projection. The descriptors only describe relative stereochemistry rather than absolute stereochemistry. All isomers are same.

Erythro / threo

[edit]

Two older prefixes still commonly used to distinguish diastereomers are threo and erythro. In the case of saccharides, when drawn in the Fischer projection the erythro isomer has two identical substituents on the same side and the threo isomer has them on opposite sides.[7] When drawn as a zig-zag chain, the erythro isomer has two identical substituents on different sides of the plane (anti). The names are derived from the diastereomeric four-carbon aldoses erythrose and threose. These prefixes are not recommended for use outside of the realm of saccharides because their definitions can lead to conflicting interpretations.[8]

Another threo compound is threonine, one of the essential amino acids. The erythro diastereomer of it is allothreonine.

 
L-Threonine (2S,3R) and D-Threonine (2R,3S)
 
L-Allothreonine (2S,3S) and D-Allothreonine (2R,3R)

Multiple stereocenters

[edit]

If a molecule contains two asymmetric centers, there are up to four possible configurations, and they cannot all be non-superposable mirror images of each other. The possibilities for different isomers continue to multiply as more stereocenters are added to a molecule. In general, the number of stereoisomers of a molecule can be determined by calculating 2n, where n = the number of chiral centers in the molecule. This holds true except in cases where the molecule has meso forms. These meso compounds are molecules that contain stereocenters, but possess an internal plane of symmetry allowing it to be superposed on its mirror image. These equivalent configurations cannot be considered diastereomers.[9]

For n = 3, there are eight stereoisomers. Among them, there are four pairs of enantiomers: R,R,R and S,S,S; R,R,S and S,S,R; R,S,S and S,R,R; and R,S,R and S,R,S. There are many more pairs of diastereomers, because each of these configurations is a diastereomer with respect to every other configuration excluding its own enantiomer (for example, R,R,R is a diastereomer of R,R,S; R,S,R; and R,S,S). For n = 4, there are sixteen stereoisomers, or eight pairs of enantiomers. The four enantiomeric pairs of aldopentoses and the eight enantiomeric pairs of aldohexoses (subsets of the five- and six-carbon sugars) are examples of sets of compounds that differ in this way.

Diastereomerism at a double bond

[edit]

Double bond isomers are always considered diastereomers, not enantiomers. Diastereomerism can also occur at a double bond, where the cis vs trans relative positions of substituents give two non-superposable isomers. Many conformational isomers are diastereomers as well.

In the case of diastereomerism occurring at a double bond, E-Z, or entgegen and zusammen (German), is used in notating nomenclature of alkenes.[10]

Applications

[edit]

As stated previously, two diastereomers will not have identical chemical properties. This knowledge is harnessed in chiral synthesis to separate a mixture of enantiomers. This is the principle behind chiral resolution. After preparing the diastereomers, they are separated by chromatography or recrystallization. Note also the example of the stereochemistry of ketonization of enols and enolates.

See also

[edit]

References

[edit]
  1. ^ IUPAC "Gold Book" diastereoisomerism  doi:10.1351/goldbook.D01679
  2. ^ Garrett, R.H.; Grisham, C.M. (2005), Biochemistry 3rd ed., Belmont CA: Thomson, p. 205, ISBN 0-534-41020-0.
  3. ^ IUPAC "Gold Book" enantiomer  doi:10.1351/goldbook.E02069
  4. ^ McCance, Robert Alexander; Madders, Kate (1930). "The comparative rates of absorption of sugars from the human intestine". Biochemical Journal. 24 (3): 795–804. doi:10.1042/bj0240795. ISSN 0264-6021. PMC 1254520. PMID 16744419.
  5. ^ Chao, Hsi-Chun; McLuckey, Scott A. (2020-10-06). "Differentiation and Quantification of Diastereomeric Pairs of Glycosphingolipids using Gas-phase Ion Chemistry". Analytical Chemistry. 92 (19): 13387–13395. doi:10.1021/acs.analchem.0c02755. ISSN 0003-2700. PMC 7544660. PMID 32883073.
  6. ^ Lavinda, Olga; Witt, Collin H.; Woerpel, K. A. (2022-03-28). "Origin of High Diastereoselectivity in Reactions of Seven-Membered-Ring Enolates". Angewandte Chemie International Edition in English. 61 (14): e202114183. doi:10.1002/anie.202114183. ISSN 1521-3773. PMC 8940697. PMID 35076978.
  7. ^ Modern physical organic chemistry Eric V. Anslyn, Dennis A. Dougherty 2006
  8. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "erythro, threo". doi:10.1351/goldbook.E02212
  9. ^ Merad, Jérémy; Candy, Mathieu; Pons, Jean-Marc; Bressy, Cyril (May 2017). "Catalytic Enantioselective Desymmetrization of Meso Compounds in Total Synthesis of Natural Products: Towards an Economy of Chiral Reagents". Synthesis. 49 (9): 1938–1954. doi:10.1055/s-0036-1589493. ISSN 0039-7881. S2CID 99010495.
  10. ^ Brown, William (2018). Organic Chemistry (8th ed.). United States: Cengage Learning. pp. 138–142. ISBN 9781305580350.