Nucleophilic Trapping of Alkoxy-Stabilized Oxyallyl Systems Generated from Inosose 2-O-Mesylates

Abstract

Protected inosose 2-O-mesylates generate oxyallyl systems by elimination of the mesylate group after enolization. The reaction is promoted by weak bases such as triethylamine and azide, and the oxyallyl systems are then trapped by nucleophilic alcohols or azide. Computations using DFT/B3LYP confirm that the singlet planar oxyallyl is stabilized by the exocyclic alkoxy group.

Key words

nucleophilic addition - carbocycle - carbohydrates - rearrangement - carbocation

• References

• 1a Harmata M. Chem. Commun. 2010; 46: 8886
• 1b Harmata M. Chem. Commun. 2010; 46: 8904
• 2 Lee JC, Jin S.-j, Cha JK. J. Org. Chem. 1998; 63: 2804
• 3 Meilert KT, Schwenter M.-E, Shatz Y, Dubbaka SR, Vogel P. J. Org. Chem. 2003; 68: 2964
• 4 Vander Wal MN, Dilger AK, MacMillan DW. C. Chem. Sci. 2013; 4: 3075
• 5 Lohse AG, Hsung RP. Chem. Eur. J. 2011; 17: 3812
• 6 Du Y, Krenske EH, Antoline JE, Lohse AG, Houk KN, Hsung RP. J. Org. Chem. 2013; 78: 1753
• 7 Krenske EH, He S, Huang J, Du Y, Houk KN, Hsung RP. J. Am. Chem. Soc. 2013; 135: 5242
• 8 Goodell JR, Poole JL, Beeler AB, Aubé J, Porco JA. J. Org. Chem. 2011; 76: 9792
• 9 Kende AS. Org. React. 1960; 11: 261
• 10 Baretta A, Waegell B In Reactive Intermediates. Springer; Berlin: 1982: 527
• 11 Loftfield RB. J. Am. Chem. Soc. 1951; 73: 4707
• 12 Hamblin GD, Jimenez RP, Sorensen TS. J. Org. Chem. 2007; 72: 8033
• 13 House HO, Thompson HW. J. Org. Chem. 1963; 28: 164
• 14 Fort AW. J. Am. Chem. Soc. 1962; 84: 4979
• 15 Fort AW. J. Am. Chem. Soc. 1962; 84: 2620
• 16 Stork G, Borowitz IJ. J. Am. Chem. Soc. 1960; 82: 4307
• 17 Stockton KP, Greatrex BW, Taylor DK. J. Org. Chem. 2014; 79: 5088
• 18 Mattox VR. J. Am. Chem. Soc. 1952; 74: 4340
• 19 Li M, Chen B, Lin M, Chan T.-M, Fu X, Rustum A. Tetrahedron Lett. 2007; 48: 3901
• 20 Spartan ’14. Wavefunction Inc; Irvine, CA: 2014. 1.1.4 ed.
• 21 Moliner V, Castillo R, Safont VS, Oliva M, Bohn S, Tuñón I, Andrés J. J. Am. Chem. Soc. 1997; 119: 1941
• 22 Chambers CC, Hawkins GD, Cramer CJ, Truhlar DG. J. Phys. Chem. 1996; 100: 16385
• 23 Ichino T, Villano SM, Gianola AJ, Goebbert DJ, Velarde L, Sanov A, Blanksby SJ, Zhou X, Hrovat DA, Borden WT. Angew. Chem. Int. Ed. 2009; 48: 8509
• 24 Reed AE, Weinstock RB, Weinhold F. J. Chem. Phys. 1985; 83: 735