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Synthesis 2012; 44(24): 3731-3734
DOI: 10.1055/s-0032-1317013
DOI: 10.1055/s-0032-1317013
practical synthetic procedures
Gram-Scale Quaternarization of the Anomeric Position of Carbohydrates: Dramatic Effects of Molecular Sieves on Rhodium(II)-Mediated Decomposition of Diazo Sugars
Further Information
Publication History
Received: 21 May 2012
Accepted after revision: 10 July 2012
Publication Date:
29 August 2012 (online)
Abstract
The optimization of rhodium(II) carbene mediated quaternarization of the anomeric position of carbohydrates is reported. Preparation of ketopyranosides in good and reliable yields requires reverse addition of the substrate to a highly diluted suspension of the catalyst in refluxing 1,2-dichloroethane, as well as addition of a carefully controlled amount of molecular sieves, and vigorous stirring. Following these optimized reaction conditions, functionalization of the anomeric position of carbohydrates can finally be performed on a preparative scale.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis. Included are 1H and 13C NMR spectra for compounds 1, 2, 4, 8, and 9.
- Supporting Information
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References
- 1 Paulissen R, Reimlinger H, Hayez E, Hubert AJ, Teyssié P. Tetrahedron Lett. 1973; 24: 2233
- 2a Ye T, McKervey MA. Chem. Rev. 1994; 94: 1091
- 2b Padwa A. Chem. Soc. Rev. 2009; 38: 3072
- 3a Padwa A, Austin DJ, Price AT, Semones MA, Doyle MP, Protopova MN, Winchester WR, Tran A. J. Am. Chem. Soc. 1993; 115: 8669
- 3b Vitale M, Lecourt T, Sheldon CG, Aggarwal VK. J. Am. Chem. Soc. 2006; 128: 2524
-
4a Doyle MP, Forbes DC. Chem. Rev. 1998; 98: 911
- 4b Davies HM. L, Beckwith RE. J. Chem. Rev. 2003; 103: 2861
- 4c Müller P. Acc. Chem. Res. 2004; 37: 243
- 5 Taber DF, Petty EH, Raman K. J. Am. Chem. Soc. 1985; 107: 196
- 6 Boultadakis-Arapinis M, Lemoine P, Turcaud S, Micouin L, Lecourt T. J. Am. Chem. Soc. 2010; 132: 15477
- 7 Toma T, Shimokawa J, Fukuyama T. Org. Lett. 2007; 9: 3195
- 8 Boultadakis-Arapinis M, Lescot C, Micouin L, Lecourt T. J. Carbohydr. Chem. 2011; 30: 587
- 9 For quantitative evaluation of molecular sieves as a drying agent for solvents, see: Williams DB. G, Lawton M. J. Org. Chem. 2010; 75: 8351
- 10 Padwa A, Dean DC, Zhi L. J. Am. Chem. Soc. 1992; 114: 593
- 11 Kumaraswamy G, Sadaiah K, Ramakrishna DS, Police N, Sridhar B, Bharatam J. Chem. Commun. 2008; 5324
For reviews, see:
For catalyst-induced chemoselective transformations, see:
For catalyst-induced stereoselective transformations, see: