Subscribe to RSS
DOI: 10.1055/s-0029-1219943
Direct α-Selective Glycosylations of Acetyl-Protected 2-Deoxy- and 2,6-Dideoxythioglycosides by Preactivation Protocol
Publication History
Publication Date:
19 May 2010 (online)
Abstract
An efficient preactivation protocol for the highly α-stereoselective glycosylation of 2-deoxy- and 2,6-dideoxysugars has been developed using acetyl-protected 2-deoxy- and 2,6-dideoxythioglycosides as glycosyl donors. The approach allows a wide range of glycosyl acceptors and donors to be used.
Key words
preactivation - α-stereoselective glycosylation - 2-deoxyglycosides - 2,6-dideoxysugars - carbohydrate
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Kirschning A.Bechthold AF.-W.Rohr J. Top. Curr. Chem. 1997, 188: 1 -
1b
Weymouth-Wilson AC. Nat. Prod. Rep. 1997, 14: 99 -
1c
Butler MS. J. Nat. Prod. 2004, 67: 2141 -
2a
Tavecchia P.Trumtel M.Veyrieres A.Sinaÿ P. Tetrahedron Lett. 1989, 30: 2533 -
2b
Perez M.Beau J.-M. Tetrahedron Lett. 1989, 30: 75 -
2c
Roush WR.Bennett CE. J. Am. Chem. Soc. 1999, 121: 3541 -
2d
Blanchard N.Roush WR. Org. Lett. 2003, 5: 81 -
2e
Roush WR.Sebesta DP.James RA. Tetrahedron 1997, 53: 8837 -
2f
Thiem J.Schottmer B. Angew. Chem., Int. Ed. Engl. 1987, 26: 555 -
2g
Marzabadi CH.Franck RW. Tetrahedron 2000, 56: 8385 -
3a
Nicolaou KC.Ladduwahetty T.Randall JL.Chucholowski A. J. Am. Chem. Soc. 1986, 108: 2466 -
3b
Zuurmond HM.van der Klein PAM.van der Marel GA.van Boom JH. Tetrahedron Lett. 1992, 33: 2063 - 4
Toshima K.Mukaiyama S.Nozaki Y.Inokuchi H.Nakata M.Tatsuta K. J. Am. Chem. Soc. 1994, 116: 9042 - 5
Rodríguez MA.Boutureira O.Matheu MI.Díaz Y.Castillón S. Eur. J. Org. Chem. 2007, 2470 -
6a
Lemieux RU.Morgan AR. Can. J. Chem. 1964, 42: 1473 -
6b
Muller T.Schneider R.Schmidt RR. Tetrahedron Lett. 1994, 35: 4763 - 7
Binkley RW.Koholic DJ. J. Org. Chem. 1989, 54: 3577 - 8
Tanaka H.Yoshizawa A.Takahashi T. Angew. Chem. Int. Ed. 2007, 46: 2505 - 9
Lear MJ.Yoshimura F.Hirama M. Angew. Chem. Int. Ed. 2001, 40: 946 - 10
Jaunzems J.Sourkouni-Argirusi G.Jesberger M.Kirschning A. Tetrahedron Lett. 2003, 44: 637 - 11
Toshima K.Nozaki Y.Tatsuta K. Tetrahedron Lett. 1991, 32: 6887 -
12a
Bielawska H.Michalska M. J. Carbohydr. Chem. 1991, 10: 107 -
12b
Laupichler L.Sajus H.Thiem J. Synthesis 1992, 1133 -
12c
Mereyala HB.Kulkarni VR.Ravi D.Sharma GVM.Rao BV.Reddy GB. Tetrahedron 1992, 48: 545 - 13
Morris WJ.Shair MD. Org. Lett. 2009, 11: 9 -
14a
Ito Y.Ogawa T. Tetrahedron Lett. 1987, 28: 2723 -
14b
Li H.Chen M.Zhao K. Tetrahedron Lett. 1997, 38: 6143 -
14c
Kim KS.Park J.Lee YJ.Seo YS. Angew. Chem. Int. Ed. 2003, 42: 459 -
15a
Yadav JS.Reddy BVS.Reddy KB.Satyanarayana M. Tetrahedron Lett. 2002, 43: 7009 -
15b
Sherry BD.Loy RN.Toste FD. J. Am. Chem. Soc. 2004, 126: 4510 -
16a
Wang Y.Ye X.-S.Zhang L.-H. Org. Biomol. Chem. 2007, 5: 2189 -
16b
Crich D.Sun S. J. Org. Chem. 1996, 61: 4506 -
16c
Crich D.Sun S. J. Org. Chem. 1997, 62: 1198 -
16d
Codée JDC.Van den Bos LJ.Litjens REJN.Overkleeft HS.Van Boom JH.Van der Marel GA. Org. Lett. 2003, 5: 1947 -
16e
Yamago S.Yamada T.Maruyama T.Yoshida J.-I. Angew. Chem. Int. Ed. 2004, 43: 2145 -
16f
Nguyen HM.Poole JL.Gin DY. Angew. Chem. Int. Ed. 2001, 40: 414 -
16g
Huang L.Wang Z.Li X.Ye X.-S.Huang X. Carbohydr. Res. 2006, 341: 1669 -
16h
Huang L.Huang X. Chem. Eur. J. 2007, 13: 529 - 17
Huang X.Huang L.Wang H.Ye X.-S. Angew. Chem. Int. Ed. 2004, 43: 5221 -
18a
Geng Y.Zhang L.-H.Ye X.-S. Chem. Commun. 2008, 597 -
18b
Geng Y.Zhang L.-H.Ye X.-S. Tetrahedron 2008, 64: 4949 - For the use of oxazolidinone functionality, also see, for example:
-
18c
Benakli K.Zha C.Kerns RJ. J. Am. Chem. Soc. 2001, 123: 9461 -
18d
Boysen M.Gemma E.Lahmann M.Oscarson S. Chem. Commun. 2005, 3044 -
18e
Manabe S.Ishii K.Ito Y. J. Am. Chem. Soc. 2006, 128: 10666 - 19
Lu Y.-S.Li Q.Zhang L.-H.Ye X.-S. Org. Lett. 2008, 10: 3445 - For the use of carbonate functionality, also see, for example:
-
20a
Crich D.Jayalath P. J. Org. Chem. 2005, 70: 7252 -
20b
Crich D.Vinod AU.Picione J. J. Org. Chem. 2003, 68: 8453 -
20c
Cotarca L.Delogu P.Nardelli A.Sunjic V. Synthesis 1996, 553 - 21
Wang C.Wang H.Huang X.Zhang L.-H.Ye X.-S. Synlett 2006, 2846 -
23a
Burgey CS.Vollerthun R.Fraser-Reid B. J. Org. Chem. 1996, 61: 1609 -
23b
Mootoo DR.Konradsson P.Udodong U.Fraser-Reid B. J. Am. Chem. Soc. 1988, 110: 5583 - 24
Zhu T.Boons G.-J. Org. Lett. 2001, 3: 4201 ; and references cited therein -
25a
Crich D.Sun S. Tetrahedron 1998, 54: 8321 -
25b
Crich D.Smith M. J. Am. Chem. Soc. 2001, 123: 9015 -
25c
Kim KS.Kim JH.Lee YJ.Lee YJ.Park J. J. Am. Chem. Soc. 2001, 123: 8477 -
25d
Tanada S.-I.Takashima M.Tokimoto H.Fujimoto Y.Tanaka K.Fukase K. Synlett 2005, 2325 -
25e
Codee JDC.Krock L.Castagner B.Seeberger PH. Chem. Eur. J. 2008, 14: 3987 -
25f
Crich D.Sharma I. Org. Lett. 2008, 10: 4731 -
25g
Crich D.Li L.-F. J. Org. Chem. 2009, 74: 773 ; and references cited therein - 26
Manabe S.Ishii K.Hashizume D.Koshino H.Ito Y. Chem. Eur. J. 2009, 15: 6894 - 27
Lin S.-C.Chao C.-S.Chang C.-C.Mong K.-KT. Tetrahedron Lett. 2010, 51: 1910 - 28
Park J.Boltje TJ.Boons G.-J. Org. Lett. 2008, 10: 4367 - 29
Xiong D.-C.Zhang L.-H.Ye X.-S. Adv. Synth. Catal. 2008, 350: 1696 ; and references cited therein
References and Notes
Typical Glycosylation
Procedure
Triflic anhydride (11.0 µL, 0.061
mmol) was added to a stirred solution of p-methylphenyl
3,4,6-tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (1a,
30.0 mg, 0.076 mmol), benzenesulfinyl morpholine (BSM, 12.9 mg,
0.061 mmol), and 4 Å MS (350 mg, activated powder) in CH2Cl2 (3.0
mL) at -72 ˚C under nitrogen atmosphere.
The reaction mixture was stirred for 10 min. After loss of 1a detected by TLC, a solution of methyl
3-O-benzyl-4,6-O-benzylidene-α-d-glucopyranoside (2a,
18.8 mg, 0.051 mmol) in CH2Cl2 (0.5 mL) was
added dropwise to the reaction mixture. The mixture was stirred
for 30 min, and the reaction was quenched by Et3N (8.0 µL).
The precipitate was filtered off, and the filtrate was concentrated.
The residue was purified by column chromatography on silica gel
(PE-EtOAc, 2.5:1) to give methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(3,4,6-tri-O-acetyl-2-deoxy-α-d-galactopyranosyl)-α-d-gluco-pyranoside (3a,
27.6 mg, 84% yield) as a foam. R
f
= 0.35 (PE-EtOAc,
1.5:1). ¹H NMR (500 MHz, CDCl3): δ = 7.50 (dd,
2 H, J = 2.0,
7.5 Hz), 7.40-7.33 (m, 7 H), 7.29-7.27 (m, 1 H),
5.60 (s, 1 H), 5.37 (ddd, 1 H, J = 3.0,
5.0, 12.5 Hz), 5.15 (d, 1 H, J = 3.0
Hz), 5.14 (d, 1 H, J = 3.5
Hz), 4.93 (d, 1 H, J = 10.5
Hz), 4.89 (d, 1 H, J = 3.5
Hz), 4.71 (d, 1 H, J = 10.5
Hz), 4.36 (t, 1 H, J = 6.5
Hz), 4.31 (dd, 1 H, J = 4.5, 10.0
Hz), 3.98 (t, 1 H, J = 9.5
Hz), 3.90 (dd, 1 H, J = 6.5, 11.0
Hz), 3.87-3.74 (m, 4 H), 3.65 (t, 1 H, J = 9.5
Hz), 3.43 (s, 3 H), 2.13-2.08 (m, 4 H), 2.00 (s, 3 H),
1.96-1.92 (m, 4 H). ¹³C NMR
(125 MHz, CDCl3): δ = 170.13, 170.23, 169.79,
138.06, 137.26, 128.96, 128.54, 128.47, 128.25, 127.86, 125.95,
101.27, 97.12, 94.10, 82.71, 76.85, 75.74, 73.45, 69.00, 66.61,
65.87, 62.25, 61.87, 55.23, 29.86, 20.81, 20.70. MS (ESI-TOF, positive): m/z = 667 [M + Na]+. Anal.
Calcd for C33H40O13: C, 61.48;
H, 6.25. Found: C, 61.65; H, 6.40.