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Two-Step Synthesis of Carbohydrates by Selective Aldol Reactions

Northrup, Alan B. and MacMillan, David W. C. (2004) Two-Step Synthesis of Carbohydrates by Selective Aldol Reactions. Science, 305 (5691). pp. 1752-1755. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20141120-095336440

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Abstract

Studies of carbohydrates have been hampered by the lack of chemical strategies for the expeditious construction and coupling of differentially protected monosaccharides. Here, a synthetic route based on aldol coupling of three aldehydes is presented for the de novo production of polyol differentiated hexoses in only two chemical steps. The dimerization of α-oxyaldehydes, catalyzed by l-proline, is then followed by a tandem Mukaiyama aldol addition-cyclization step catalyzed by a Lewis acid. Differentially protected glucose, allose, and mannose stereoisomers can each be selected, in high yield and stereochemical purity, simply by changing the solvent and Lewis acid used. The reaction sequence also efficiently produces ^(13)C-labeled analogs, as well as structural variants such as 2-amino– and 2-thio–substituted derivatives.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.1101710 DOIArticle
http://www.sciencemag.org/content/305/5691/1752PublisherArticle
http://www.sciencemag.org/content/305/5691/1752/suppl/DC1PublisherSupporting Online Material
Additional Information:© 2004 American Association for the Advancement of Science. 21 June 2004; accepted 22 July 2004; published online 12 August 2004. Financial support was provided by the NIH National Institute of General Medical Sciences (R01 GM66142-01) and gifts from Bristol-Myers Squibb, Johnson and Johnson, Eli Lilly, and Merck Research Laboratories. D.W.C.M. is grateful for support from the Camille and Henry Dreyfuss Foundation, the Sloan Foundation, and Research Corporation under the Cottrell Scholarship and Research Innovation programs. A.B.N. is grateful for an NSF predoctoral fellowship.
Funders:
Funding AgencyGrant Number
NIHR01 GM66142-01
Bristol-Myers SquibbUNSPECIFIED
Johnson and JohnsonUNSPECIFIED
Eli LillyUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
NSF predoctoral fellowshipUNSPECIFIED
Merck Research LaboratoriesUNSPECIFIED
Issue or Number:5691
Record Number:CaltechAUTHORS:20141120-095336440
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141120-095336440
Official Citation:Northrup, A. B., & MacMillan, D. W. C. (2004). Two-Step Synthesis of Carbohydrates by Selective Aldol Reactions. Science, 305(5691), 1752-1755. doi: 10.1126/science.1101710
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:51994
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:20 Nov 2014 19:26
Last Modified:03 Oct 2019 07:38

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