Interrupted Pummerer Reaction in Latent/Active Glycosylation

In memory of Professor Shuzheng Zhang

Abstract

A latent/active glycosylation strategy is efficient for rapid ­assembly of oligosaccharides. We recently developed novel OPTB/OPSB and SPTB/SPSB glycosides as two pairs of latent/active glycosyl donors. The active OPSB and SPSB glycosyl donors are efficiently activated by Tf₂O via an interrupted Pummerer reaction mechanism. In this account, the design, developments, mechanism studies and applications of these new glycosylation methodologies are described.

1 Introduction

2 Conceiving Ideas

3 Synthesis of OPSB and SPSB Glycosides

4 Substrate Scope

5 Application in the Synthesis of Natural Products

6 Conclusion

Key words

interrupted Pummerer reaction - glycosylation - carbo­hydrate - latent/active - sulfoxide - total synthesis - natural products

• References

• 1a Boons G.-J. Tetrahedron 1996; 52: 1095
• 1b Smoot JT. Demchenko AV. Adv. Carbohydr. Chem. Biochem. 2009; 62: 161
• 1c Zhu X. Schmidt RR. Angew. Chem. Int. Ed. 2009; 48: 1900
• 1d Kaeothip S. Demchenko AV. Carbohydr. Res. 2011; 346: 1371
• 1e Boltje TJ. Buskas T. Boons G.-J. Nat. Chem. 2009; 1: 611
• 1f Yang Y. Zhang X. Yu B. Nat. Prod. Rep. 2015; 32: 1331
• 2 Roy R. Andersson FO. Letellier M. Tetrahedron Lett. 1992; 33: 6053
• 3 Fraser-Reid B. Udodong UE. Wu Z. Ottosson H. Merritt JR. Rao CS. Roberts C. Madsen R. Synlett 1992; 927
• 4 Boons G.-J. Isles S. Tetrahedron Lett. 1994; 35: 3593
• 5 Kim KS. Kim JH. Lee YJ. Lee YJ. Park J. J. Am. Chem. Soc. 2001; 123: 8477
• 6 Huang L. Wang Z. Huang X. Chem. Commun. 2004; 1960
• 7 Wang P. Haldar P. Wang Y. Hu H. J. Org. Chem. 2007; 72: 5870
• 8 Hasty SJ. Kleine MA. Demchenko AV. Angew. Chem. Int. Ed. 2011; 50: 4197
• 9 Chen X. Shen D. Wang Q. Yang Y. Yu B. Chem. Commun. 2015; 51: 13957
• 10 Cremlyn RJ. An Introduction to Organosulfur Chemistry . John Wiley & Sons; Chichester: 1996: 63-79

Selected references:
• 11a Pummerer R. Chem. Ber. 1909; 42: 2282
• 11b Pummerer R. Chem. Ber. 1910; 43: 1401
• 11c Bur SK. Padwa A. Chem. Rev. 2004; 104: 2401
• 11d Akai S. Kita Y. Recent Advances in Pummerer Reactions. In Topics in Current Chemistry: Sulfur-Mediated Rearrangements I. Schaumann E. Springer-Verlag; Berlin: 2007. 274, 35
• 11e Smith LH. S. Coote SC. Sneddon HF. Procter DJ. Angew. Chem. Int. Ed. 2010; 49: 5832

Selected references:
• 12a Pfitzner KE. Moffatt JG. J. Am. Chem. Soc. 1963; 85: 3027
• 12b Epstein WW. Sweat FW. Chem. Rev. 1967; 67: 247

Selected references:
• 13a Corey EJ. Kim CU. J. Am. Chem. Soc. 1972; 94: 7586
• 13b Mancuso AJ. Huang S.-L. Swern D. J. Org. Chem. 1978; 43: 2480
• 13c Omura K. Swern D. Tetra­hedron 1978; 34: 1651
• 13d Mancuso AJ. Brownfain DS. Swern D. J. Org. Chem. 1979; 44: 4148
• 13e Mancuso AJ. Swern D. ­Synthesis 1981; 165
• 13f Tidwell TT. Synthesis 1990; 857
• 14 Kahne D. Walker S. Cheng Y. Van Engen D. J. Am. Chem. Soc. 1989; 111: 6881
• 15 Crich D. Sun S. J. Org. Chem. 1996; 61: 4506
• 16 Garcia BA. Poole JL. Gin DY. J. Am. Chem. Soc. 1997; 119: 7597
• 17 Di Bussolo V. Kim Y.-J. Gin DY. J. Am. Chem. Soc. 1998; 120: 13515
• 18 Shu P. Yao W. Xiao X. Sun J. Zhao X. Zhao Y. Xu Y. Tao J. Yao G. Zeng J. Wan Q. Org. Chem. Front. 2016; 3: 177
• 19 Shu P. Xiao X. Zhao Y. Xu Y. Yao W. Tao J. Wang H. Yao G. Lu Z. Zeng J. Wan Q. Angew. Chem. Int. Ed. 2015; 54: 14432
• 20 Xiao X. Zhao Y. Shu P. Zhao X. Liu Y. Sun J. Zhang Q. Zeng J. Wan Q. J. Am. Chem. Soc. 2016; 138: 13402
• 21 Zeng J. Sun G. Yao W. Zhu Y. Wang R. Cai L. Liu K. Zhang Q. Liu X.-W. Wan Q. Angew. Chem. Int. Ed. 2017; 56: 5227
• 22 Shu P. Zeng J. Tao J. Zhao Y. Yao G. Wan Q. Green Chem. 2015; 17: 2545
• 23 Xu Y. Zhang Q. Xiao Y. Wu P. Chen W. Song Z. Xiao X. Meng L. Zeng J. Wan Q. Tetrahedron Lett. 2017; 58: 2381

Bz was used as a protecting group instead of Ac to avoid the acyl transfer side reactions:
• 24a Kovác P. Carbohydr. Res. 1986; 153: 237
• 24b Nukada T. Berces A. Whitfield DM. J. Org. Chem. 1999; 64: 9030
• 24c Deng S. Yu B. Xie J. Hui Y. J. Org. Chem. 1999; 64: 7265
• 24d Xiong D. Zhang L. Ye X. Adv. Synth. Catal. 2008; 350: 1696
• 24e Xiong D. Yang A. Yu Y. Ye X. Tetrahedron Lett. 2015; 56: 211
• 25a Zhou B.-N. Bahler BD. Hofmann GA. Mattern MR. Johnson RK. Kingston DG. I. J. Nat. Prod. 1998; 61: 1410
• 25b Zhang F. Yang Y.-N. Song X.-Y. Shao S.-Y. Feng Z.-M. Jiang J.-S. Li L. Chen N.-H. Zhang P.-C. J. Nat. Prod. 2015; 78: 2390
• 26a Sugaya K. Hashimoto F. Ono M. Ito Y. Masuoka C. Nohara T. Food Sci. Technol. Int. 1998; 4: 278
• 26b Li Y. Chen Z. Feng Z. Yang Y. Jiang J. Zhang P. Carbohydr. Res. 2012; 348: 42