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Aldol

From Wikipedia, the free encyclopedia
Organic compound of the form R–CH(OH)–CHR–C(=O)–R
General aldol structure showing the α and 𝛽 positions of carbons relative to the carbonyl. When R" is -H, it is an aldol, when R" is a carbon, it is a ketol.

Inorganic chemistry, analdol is a structure consisting of ahydroxy group (-OH) two carbons away from either analdehyde or aketone. The name combines the suffix 'ol' from the alcohol and the prefix depending on thecarbonyl group, either 'ald' for an aldehyde, or 'ket' for a ketone, in which case it referred to as a 'ketol'. An aldol may also use the term β-hydroxy aldehyde (or β-hydroxy ketone for a ketol). The term "aldol" may refer to3-hydroxybutanal.[1][2]

Aldols are the product of acarbon-carbon bond-formation reaction, giving them wide applicability as a precursor for a variety of other compounds.

Synthesis and reactions

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Possiblestereochemical configurations for chiral aldols. R/S configurations ofchiral centers: A: OH is 4R, R-group is 3R B: OH is 4S, R-group is 3S C: OH is 4R, R-group is 3S D: OH is 4S, R-group is 3R

Aldols are usually synthesized from analdol addition reaction using two aldehydes or an aldehyde and a ketone for a ketol.[1] These reactions may also be done intramolecularly to form 5 or 6 member rings or for stereoselective syntheses in the active area ofasymmetric synthesis.

Aldols may also undergo acondensation reaction in which the hydroxy group is replaced by api bond. The final structure is a reactiveα,β-unsaturated carbonyl compound, which can also be used in a variety of other reactions:

RC(O)CH2CH(OH)R' → RC(O)CH=CHR' + H2O

Applications

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Aldols synthesized from two aldehydes are usually unstable, often producing secondary compounds such asdiols,unsaturated aldehydes, oralcohols.[1]Hydroxypivaldehyde is a rare example of adistillable aldol.[3] The aldol3-hydroxybutanal is a precursor toquinaldine, which is a precursor to the dyequinoline Yellow SS.[1]

Aldols are also used as intermediates in the synthesis ofpolyketide natural products and drugs such asOseltamivir andEpothilone.[4][5][6][7]

See also

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References

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  1. ^abcdKohlpainter, Christian; Schulte, Markus; Falbe, Jürgen; Lappe, Peter; Weber, Jürgen; Frey, Guido D. (15 January 2013)."Aldehydes, Aliphatic".Ullmann's Encyclopedia of Industrial Chemistry (7).doi:10.1002/14356007.a01_321.pub3.ISBN 9783527303854. Retrieved1 April 2023 – via Wiley Online Library.
  2. ^PubChem."CID 21282929".National Center for Biotechnology Information. Retrieved2023-04-15.
  3. ^Zhang, Yanping; Mu, Hongliang; Pan, Li; Wang, Xuling; Li, Yuesheng (21 May 2018). "Robust Bulky [P,O] Neutral Nickel Catalysts for Copolymerization of Ethylene with Polar Vinyl Monomers".ACS Catal.8 (7):5963–5976.doi:10.1021/acscatal.8b01088 – via ACS Publications.
  4. ^Schetter, Bernd; Mahrwald, Rainer (2006). "Modern aldol methods for the total synthesis of polyketides".Angewandte Chemie International Edition.45 (45):7506–25.doi:10.1002/anie.200602780.PMID 17103481.
  5. ^Ghosh, Arun K.; Dawson, Zachary L. (2009)."Synthesis of Bioactive Natural Products by Asymmetric syn- and anti-Aldol Reactions".Synthesis.2009 (17):2992–3002.doi:10.1055/s-0029-1216941.PMC 6233898.PMID 30443084 – via Thieme.
  6. ^Ko, Ji S.; Keum, Ji E.; Ko, Soo Y. (15 October 2010)."A synthesis of oseltamivir (Tamiflu) starting from D-mannitol".J Org Chem.75 (20):7006–9.doi:10.1021/jo101517g.PMID 20866058 – via National Library Of Medicine.
  7. ^Schinzer, Dieter (2004-06-24), Mahrwald, Rainer (ed.),"The Aldol Reaction in Natural Product Synthesis: The Epothilone Story",Modern Aldol Reactions (1 ed.), Wiley, pp. 311–328,doi:10.1002/9783527619566.ch7,ISBN 978-3-527-30714-2, retrieved2024-04-15
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