for Propargyl/Methyl Furanosides as Potential Glycosyl Donors

Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011
Supporting Information for
Propargyl/Methyl Furanosides as Potential Glycosyl Donors
Srinivasa Rao Vidadala,a Gaddamannugu Gayatrib, G. Narahari Sastry*b and Srinivas Hotha*c [email protected], [email protected]

Contents
General Experimental Techniques General Experimental Procedures Compound Characterization Data 1H, 13C and DEPT NMR Spectral Charts of all Compounds Computational details: Structure and energies of various conformations considered.

Page Number
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General Experimental Techniques
Unless otherwise noted, materials were obtained from commercial suppliers and were used without further purification. Unless otherwise reported all reactions were performed under argon atmosphere. Removal of solvent in vacuo refers to distillation using a rotary evaporator attached to an efficient vacuum pump. Products obtained as solids or syrups were dried under high vacuum. AuBr3 was purchased from multi-national commercial vendors. Analytical thinlayer chromatography was performed on pre-coated silica plates (F254, 0.25 mm thickness); compounds were visualized by UV light or by staining with anisaldehyde spray. Optical rotations were measured on a JASCO P-1020 polarimeter. IR spectra were recorded on a Perkin-Elmer 1600 FT-IR spectrometer. NMR spectra were recorded either on a Bruker AC 200, AV 400 or AV 500 with CDCl3 as the solvent and internal standard. Elemental analyses were performed on an ELEMENTAR vario EL analysator. High resolution mass spectroscopy (HRMS) was performed on MALDI-TOF using 2,5-dihydroxybenzoic acid as the solid matrix. Low resolution mass spectroscopy (LRMS) was performed on Waters Acquity UPLC-MS.
General Experimental Procedures
General Procedure for AuBr3-mediated transfuranosylations using propargyl furanosides as glycosyl donors: To a solution of glycosyl donor (0.2 mmol) and aglycone (0.22 mmol) in anhydrous acetonitrile (5 mL) was added 8 mol% of AuBr3 and AgOTf under argon atmosphere at room temperature. The resulting mixture was stirred at room temperature until TLC showed complete conversion. The reaction mixture was concentrated in vacuo to obtain a crude residue which was purified by silica gel column chromatography using ethyl acetate-petroleum ether as mobile phase.
General Procedure for AuBr3-mediated transfuranosylations using methyl furanosides as glycosyl donors: To a solution of glycosyl donor (0.2 mmol) and aglycone (0.22 mmol) in anhydrous acetonitrile (5 mL) was added 8 mol% of AuBr3 and AgOTf under argon atmosphere at room temperature. The resulting mixture was stirred at 65oC until TLC showed complete conversion. The reaction mixture was concentrated in vacuo to obtain a crude residue which was purified by silica gel column chromatography using ethyl acetate-petroleum ether as mobile phase.
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Compound Characterization Data
Compound 1a:
[α]D(CHCl3, c 1.6) = -37.6; 1H NMR (200.13 MHz, CDCl3): δ 2.37(t, 1H, J = 2.4Hz), 3.48(dd, 1H, J = 5.4, 10.6Hz), 3.62(dd(1H, J = 3.3, 10.6Hz), 3.90(d, 1H, J = 4.9Hz), 4.07(dd, 1H, J = 4.6, 7.4Hz), 4.15(d, 2H, J = 2.3Hz), 4.31-4.71(m, 5H), 4.54(ABq, 2H, J = 11.8Hz), 5.21(s, 1H), 7.167.40(m, 15H) ; 13C NMR (55.32 MHz, CDCl3): δ 53.9, 70.6, 72.2, 72.3, 72.9, 74.5, 78.0, 79.0, 79.4, 80.5, 103.0, 127.4-128.3, 137.6, 137.6, 138.1; Mol. Wt. calculated for C29H30O5Na: 481.535, Found: 481.512.
Compound 1b:
[α]D(CHCl3, c 1.3) = +52.2; 1H NMR (200.13 MHz, CDCl3): δ 2.41(t, 1H, J = 2.4Hz), 3.70(dd, 1H, J = 7.2, 10.2Hz), 3.77(dd, 1H, J = 4.8, 10.1Hz), 4.06(s, 1H), 4.08(dd, 1H J = 2.8, 8.3Hz), 4.27(dd, 2H, J = 1.4, 2.3Hz), 4.42-4.61(m, 6H), 4.45(dd, 1H, J = 3.3, 5.1Hz), 5.27(s, 1H), 7.227.38(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 54.5, 69.6, 71.9, 72.1, 73.4, 74.5, 79.2, 80.4, 81.6, 86.6, 104.8, 127.5-128.4, 137.4, 137.7, 138.2; Mol. Wt. calculated for C29H30O5Na: 481.535, Found: 481.449.
Compound 1c:
[α]D(CHCl3, c 1.6) = -20.4; 1H NMR (200.13 MHz, CDCl3): δ 2.41(t, 1H, J = 2.4Hz), 3.60(d, 1H, J = 2.4 Hz), 3.62(d, 1H, J = 1.0Hz), 3.92(dd, 1H, J = 3.0, 6.6Hz), 4.05(dd, 1H J = 0.9, 3.0Hz), 4.22(m, 1H), 4.28(d, 2H, J = 2.2Hz), 4.51(ABq, 2H, J = 12.0), 4.53(ABq, 2H, J = 12.0Hz), 4.56(s, 2H), 5.32(s, 1H), 7.22-7.32(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 54.0, 69.6, 71.9, 72.1, 73.4, 74.4, 79.2, 81.1, 83.4, 88.0, 104.2, 127.6-128.4, 137.4, 137.7, 138.0; Mol. Wt. calculated for C29H30O5Na: 481.535, Found: 481.510.
Compound 1d:
[α]D(CHCl3, c 1.5) = +29.4; 1H NMR (200.13 MHz, CDCl3): δ 2.40(t, 1H, J = 2.4Hz), 3.77(d, 2H, J = 5.9Hz), 3.94(dd, 1H, J = 2.0, 4.6Hz), 4.23(dd, 2H, J = 2.4, 5.0Hz), 4.34(t, 1H, J = 5.9Hz), 4.46(d,1H, J = 0.7Hz), 4.52(s, 2H), 4.60(dd, 2H, J = 7.4, 12.0Hz), 4.68(dd, 2H, J = 4.5, 12.1Hz), 5.31(d, 1H, J = 2.0Hz), 7.22-7.34(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 54.7, 69.6, 72.4, 73.1, 73.3, 74.4, 77.8, 78.5, 79.2, 82.1, 103.5, 127.5-128.3, 137.7, 137.9, 138.1; Mol. Wt. calculated for C29H30O5Na: 481.535, Found: 481.510.
Compound 3a:
[α]D(CHCl3, c 1.2) = +42.9; 1H NMR (200.13 MHz, CDCl3): δ 3.38(s, 3H), 3.46-3.65(m, 1H), 3.51(dd, 1H, J = 5.7, 10.5Hz), 3.62(dd, 1H, J = 4.1, 10.5Hz), 3.91(dd, 1H, J = 2.2, 11.5Hz), 3.95(d, 1H, J = 4.9Hz), 4.02(dd, 1H, J = 4.7, 7.3Hz), 4.14(qd, 1H, J = 2.5, 9.9Hz), 4.31(dd, 1H, J
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= 3.5, 6.1Hz), 4.45(ABq, 2H, J = 11.9Hz), 4.51(s, 2H), 4.66(d, 2H, J =4.4Hz), 5.00(s, 1H), 5.16(dd, 1H J = 3.6, 8.4Hz), 5.23(dd, 1H, J = 3.6, 14.9Hz), 5.58(t, 1H, J = 9.9Hz), 6.12(t, 1H, 9.9Hz), 7.21-7.55(m, 24H), 7.85-8.00(m, 6H) ; 13C NMR (55.32 MHz, CDCl3): δ 55.4, 66.1, 68.6, 69.3, 70.6, 71.4, 72.1, 72.3, 73.1, 77.2, 78.2, 79.3, 80.6, 96.9, 106.0, 127.5-129.9, 13.1, 133.3, 133.4, 137.8, 137.9, 138.3, 165.2, 165.8, 165.8; Mol. Wt. calculated for C54H52O13Na: 931.973, Found: 931.909.
Compound 3b:
[α]D(CHCl3, c 1.8) = +11.8; 1H NMR (200.13 MHz, CDCl3): δ 1.68(m, 2H), 2.11(m, 2H), 3.25-3.60(m, 4H), 3.92(dd, 1H, J = 3.1, 6.8Hz), 4.03(dd, 1H, J = 1.2, 3.3Hz), 4.05-4.25(m, 2H), 4.44-4.67(m, 6H), 4.96(dq, 1H, J = 1.0, 8.8Hz), 5.04(s, 1H), 5.80(m, 1H), 7.22-7.36(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 28.6, 30.2, 67.2, 71.4, 72.2, 72.3, 73.1, 78.5, 79.7, 80.3, 105.2, 114.7, 127.4-128.3, 129.6, 137.8, 138.1, 138.2; Mol. Wt. calculated for C31H36O5Na: 511.604, Found: 511.551.
Compound 3c:
[α]D(CHCl3, c 1.0) = -20.8; 1H NMR (200.13 MHz, CDCl3): δ 0.70(d, 3H, J = 7.0Hz), 0.81, 0.84, 0.88, 0.91(4s, 6H), 1.28(m, 3H), 1.61(m, 4H), 2.03(m, 2H), 3.40(dd, 1H, J = 4.0, 10.5Hz), 3.49(dd, 1H, J = 6.6, 10.4Hz), 3.61(dd, 1H, J = 4.0, 10.4Hz), 3.80(dd, 1H, J = 1.2, 4.7Hz), 3.91(m, 1H), 4.36(dt, 1H, J = 4.1, 7.0Hz), 4.52(dd, 2H, J = 11.7, 18.7Hz), 4.55(d, 2H, J = 1.8Hz), 4.64(s, 2H), 5.21(d, 1H, J = 0.7Hz), 7.25-7.39(m, 15H) ; 13C NMR (55.32 MHz, CDCl3): δ 15.9, 21.1, 22.3, 23.0, 25.1, 29.7, 31.3, 34.4, 39.8, 47.9, 72.0, 72.3, 73.1, 75.3, 78.8, 79.7, 80.4, 101.6, 127.5-128.4, 137.8, 138.0, 138.3; Mol. Wt. calculated for C36H46O5Na: 581.737, Found: 581.235.
Compound 3d:
[α]D(CHCl3, c 1.5) = +5.3; 1H NMR (200.13 MHz, CDCl3): δ 3.29(s, 3H), 3.31-3.65(m, 5H), 3.72(dd, 1H, J = 4.0, 9.7Hz), 3.89(dt, 1H, J = 0.9, 4.7Hz), 3.90-4.05(m, 3H), 4.33(dd, 1H, J = 5.7, 10.8Hz), 4.41-4.65(m, 8H), 4.72(ABq, 2H, J = 12.2Hz), 4.82(t, 1H, J = 10.9Hz), 4.88(ABq, 2H, J = 10.8Hz), 5.06(d, 1H, J = 0.8Hz), 7.22-7.33(m, 30H) ; 13C NMR (55.32 MHz, CDCl3): δ 55.0, 66.5, 69.9, 71.3, 72.2, 72.3, 73.1, 73.3, 74.9, 75.7, 77.9, 78.3, 79.7, 78.8, 80.5, 82.0, 97.8, 105.7, 127.4-128.4, 137.7, 137.7, 138.1, 138.1, 138.2, 138.6 ; Mol. Wt. calculated for C54H58O10Na: 890.022, Found: 889.903.
Compound 3e:
[α]D(CHCl3, c 1.3) = +48.1; 1H NMR (200.13 MHz, CDCl3): δ 3.44-3.52(m, 2H), 3.60(dd, 1H, J = 3.5, 10.6Hz), 3.70(dd, 1H J = 1.2, 4.6Hz), 3.73-3.83(m, 2H), 4.00(dd, 1H, J = 4.8, 6.6Hz), 4.16(dd, 1H, J = 2.0, 11.6Hz), 4.27(ABq, 2H, J = 11.9Hz), 4.30(dd, 1H , J = 3.0, 7.9Hz), 4.47(d,
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1H, J = 1.4Hz), 4.50(ABq, 2H, J = 11.6Hz), 4.56(s, 2H), 4.80(s, 2H), 4.95(d, 1H, J = 1.1Hz), 5.11(s, 2H), 5.36(d, 1H, J = 8.1Hz), 5.91(d, 1H, J = 1.0Hz), 7.14-7.38(m, 30H), 7.51(d, 1H, J = 1.7Hz), 7.58(d, 2H, J = 8.1Hz) ; 13C NMR (55.32 MHz, CDCl3): δ 43.9, 65.5, 70.0, 71.3, 72.0, 72.4, 73.3, 74.0, 77.4, 78.1, 79.7, 80.8, 80.9, 89.2, 100.9, 105.8, 127.5-128.7, 129.3, 136.7, 137.2, 137.2, 137.4, 137.4, 137.5, 137.8, 150.6, 162.4 ; Mol. Wt. calculated for C56H56N2O10Na: 940.0410, Found: 939.899.
Compound 3f:
[α]D(CHCl3, c 2.1) = +61.3; 1H NMR (200.13 MHz, CDCl3): δ 2.34(t, 1H, J = 2.3Hz), 3.423.67(m, 3H), 3.85-4.00(m, 2H), 4.04(dd, 1H, J = 4.6, 7.2Hz), 4.15-4.55(m, 8H), 4.66(d, 2H, J = 3.6Hz), 4.99(s, 1H), 5.31(dd, 1H J = 3.7Hz), 5.50(dd, 1H, J = 3.5Hz), 5.61(t, 1H, J = 9.9Hz), 6.13(t, 1H, J = 10.0Hz), 7.24-7.56(m, 24H), 7.85-8.01(m, 6H) ; 13C NMR (55.32 MHz, CDCl3): δ 55.2, 66.0, 69.1, 69.2, 70.4, 71.3, 71.6, 72.1, 72.3, 73.1, 75.3, 78.2, 78.3, 79.3, 80.6, 94.7, 106.0, 127.5-129.9, 133.1, 133.3, 133.4, 137.8, 137.9, 138.2, 165.2, 165.7, 165.8 ; Mol. Wt. calculated for C56H52O13Na: 955.994, Found: 955.545.
Compound 4a(/):
1H NMR (500.13 MHz, CDCl3): δ 3.35(s, 3H), 3.46-3.54(m, 2H), 3.43(s, 3H), 3.60-3.79(m, 6H), 3.94-4.10(m, 6H), 4.20-4.25(m, 2H), 4.35-4.68(m, 12H), 5.04(s, 1H), 5.08(s, 1H), 5.195.27(m, 4H), 5.59(t, 1H. J = 9.8Hz), 5.69(t, 1H, J = 9.8Hz), 6.10-6.16(m, 2H), 7.23-7.52(m, 48H), 7.86-7.99(m, 12H); 13C NMR (125.76 MHz, CDCl3): δ 55.3, 55.5, 65.7, 66.5, 68.7, 68.8, 69.1, 69.3, 69.3, 69.7, 70.6, 70.7, 71.8, 71.9, 72.0, 72.2, 72.3, 72.7, 73.2, 73.3, 79.8, 80.2, 81.5, 81.9, 86.6, 86.7, 96.8, 96.9, 101.7, 107.5, 127.5-129.9, 133.0, 133.0, 133.2, 133.3, 133.3, 133.3, 137.5, 137.7, 137.8, 137.9, 138.3, 138.3, 165.1, 165.2, 165.8, 165.8, 165.8, 165.9 ; Mol. Wt. calculated for C54H52O15Na: 931.973, Found: 931.769.
Compound 4b(/):
1H NMR (200.13 MHz, CDCl3): δ 1.68(m, 4H), 2.13(m, 4H), 3.25-3.80, 8H), 3.92(dd, 1H, J = 3.3, 6.8Hz), 4.03(dd, 1H, J = 1.2, 3.2Hz), 4.05-4.12(m, 2H), 4.16-4.24(m, 2H), 4.44-4.68(m, 12H), 4.85-5.10(m, 6H), 5.68-5.93(m, 2H), 7.20-7.45(m, 30H); 13C NMR (55.32 MHz, CDCl3): δ 28.6, 28.7, 29.6, 30.2, 66.8, 67.2, 69.7, 71.9, 72.0, 72.2, 72.4, 72.6, 73.3, 73.3, 80.1, 80.4, 83.4, 83.5, 84.2, 88.3, 100.5, 106.1, 114.8, 114.8, 127.5-128.4, 137.5, 137.7, 137.9, 138.0, 138.1, 138.1, 138.2, 138.2 ; Mol. Wt. calculated for C31H36O5Na: 511.604, Found: 511.550.
Compound 4c(/):
1H NMR (200.13 MHz, CDCl3): δ 0.69-0.92(m, 22H), 0.95-1.49(m, 6H), 1.54-1.70(m, 4H), 2.05-2.40(m, 4H), 3.30-3.58(m, 2H), 3.60-3.85(m, 4H), 3.96-4.05(m, 4H), 4.30-4.70(m, 14H), 5.17(d, 1H, J = 4.3Hz), 5.25(s, 1H), 7.18-7.40(m, 30H) ; 13C NMR (55.32 MHz, CDCl3): δ
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15.8, 15.9, 21.1, 21.1, 22.2, 22.4, 22.8, 23.0, 24.8, 25.1, 31.3, 31.7, 34.3, 34.5, 39.6, 43.2, 48.0, 48.0, 48.4, 69.5, 71.8, 71.9, 72.5, 72.6, 73.3, 73.3, 74.8, 75.5, 80.0, 80.2, 81.4, 81.7, 84.4, 86.3, 100.8, 102.8, 127.4-128.4, 137.8, 138.1, 138.2, 138.3, 138.3, 138.4; Mol. Wt. calculated for C36H46O5Na: 581.737, Found: 581.236.
Compound 4d(/):
1H NMR (200.13 MHz, CDCl3): δ 3.28(s, 3H), 3.34(s, 3H), 3.35(dd, 1H, J = 9.4, 16.8Hz), 3.43(dd, 1H, J = 3.7, 9.5Hz), 3.49(ABq, 2H, J = 9.4Hz), 3.57(dd, 2H, J = 6.7, 10.7Hz), 3.633.80(m, 8H), 3.96-4.13(m, 8H), 4.28(dd, 1H, J = 5.8, 7.0Hz), 4.37(m, 1H), 4.42-4.88(m, 22H), 4.93-4.98(m, 2H), 5.07(d, 1H, J = 1.5Hz), 5.13(d, 1H, J = 4.3Hz), 7.20-7.38(m, 60H); 13C NMR (55.32 MHz, CDCl3): δ 55.0, 55.1, 66.5, 66.9, 69.3, 69.6, 70.0, 70.2, 71.9, 72.1, 72.1, 72.4, 73.3, 73.3, 73.4, 73.4, 75.0, 75.1, 75.6, 75.7, 76.2, 77.8, 78.1, 80.0, 80.0, 80.0, 81.6, 81.8, 82.0, 82.0, 83.6, 86.7, 97.9, 98.1, 100.5, 107.3, 127.5-128.4, 137.5, 137.8, 138.0, 138.1, 138.2, 138.2, 138.2, 138.2, 138.3, 138.3, 138.7, 138.9 ; Mol. Wt. calculated for C54H58O10Na: 890.022, Found: 890.811.
Compound 5a:
[α]D(CHCl3, c 1.3) = +0.8; 1H NMR (200.13 MHz, CDCl3): δ 3.38(s, 3H), 3.44-3.68(m, 3H), 3.75-4.20(m, 4H), 4.27-4.80(m, 3H), 4.46(ABq, 2H, J = 11.8Hz), 4.66(ABq, 2H, J = 11.8Hz), 5.01(s, 1H), 5.22(dd, 1H, J = 3.5, 9.4Hz), 5.25(dd, 1H, J = 3.5, 19.5Hz), 5.59(t, 1H, J = 9.8Hz), 6.13(t, 1H, J = 9.8Hz), 7.24-7.50(m, 24H), 7.86-8.00(m, 6H); 13C NMR (55.32 MHz, CDCl3): δ 55.4, 66.1, 68.6, 69.2, 70.5, 71.3, 72.0, 72.0, 72.2, 73.0, 78.2, 79.2, 80.5, 96.8, 105.9, 127.4129.8, 133.0, 133.3, 133.3, 137.8, 137.8, 138.2, 165.2, 165.7, 165.8 ; Mol. Wt. calculated for C54H52O13Na: 931.973, Found: 931.916.
Compound 5b(/):
1H NMR (200.13 MHz, CDCl3): δ 1.57(m, 4H), 2.03(m, 4H), 3.20-3.78(m, 8H), 3.86(dd, 1H, J = 0.8, 4.5Hz), 4.01(dd, 1H, J = 4.7, 7.0Hz), 4.10-4.40(m, 4H), 4.42-4.72(m, 12H), 4.90-5.15(m, 6H), 5.59-5.90(m, 2H), 7.21-7.60(m, 30H); 13C NMR (55.32 MHz, CDCl3): δ 28.5, 28.6, 29.6, 30.2, 66.8, 67.2, 69.6, 69.7, 71.9, 72.0, 72.2, 72.3, 72.6, 73.3, 80.1, 80.3, 83.4, 84.1, 88.2, 88.3, 100.5, 106.0, 114.8, 114.8, 127.5-128.4, 137.5, 137.6, 137.8, 137.9, 138.0, 138.0, 138.0, 138.1 ; Mol. Wt. calculated for C31H36O5Na: 511.604, Found: 511.551.
Compound 5c:
[α]D(CHCl3, c 1.2) = +14.4; 1H NMR (200.13 MHz, CDCl3): δ 0.79(d, 3H, J = 6.9Hz), 0.87, 0.90, 0.90, 0.94(4s, 6H), 1.01(m, 2H), 1.25(m, 3H), 1.63(m, 2H), 2.16(m, 2H), 3.36(dt, 1H, J = 4.3, 10.4Hz), 3.63(t, 1H, J = 10.9Hz), 3.63(dd, 1H, J = 10.9, 19.8Hz), 3.90(dd, 1H, J = 3.3, 7.1Hz), 4.03(dd, 1H, J = 1.2, 3.4Hz), 4.25(m, 1H), 4.51(ABq, 2H, J = 11.9Hz), 4.52(ABq, 2H, J
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= 11.8Hz), 4.56(d, 2H, J = 1.5Hz), 5.16(s, 1H), 7.26-7.32(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 16.1, 21.2, 22.2, 23.0, 25.6, 31.6, 34.3, 43.3, 48.4, 69.7, 71.9, 72.0, 73.2, 79.7, 80.0, 83.7, 88.6, 107.6, 127.5-128.4, 137.6, 138.0, 138.2; Mol. Wt. calculated for C36H46O5Na: 581.737, Found: 581.423.
Compound 5d:
[α]D(CHCl3, c 2.3) = +24.4; 1H NMR (200.13 MHz, CDCl3): δ 3.36(s, 3H), 3.47-3.78(m, 5H), 3.97(dd, 2H, J = 8.8, 17.2Hz), 4.04-4.15(m, 2H), 4.20(dd, 1H, J = 4.9, 9.5Hz), 4.40-4.65(m, 8H), 4.74(ABq, 2H, J = 3.7Hz), 4.76(t, 2H, J = 8.6Hz), 4.89(ABq, 2H, J = 11.0Hz), 5.18(s, 1H), 7.237.33(m, 30H) ; 13C NMR (55.32 MHz, CDCl3): δ 55.1, 65.7, 69.6, 69.9, 71.7, 72.0, 73.2, 73.3, 75.0, 75.9, 77.6, 79.8, 81.1, 82.0, 83.2, 87.8, 98.1, 106.7, 127.5-128.4, 137.4, 137.7, 138.0, 138.1, 138.3, 138.8 ; Mol. Wt. calculated for C54H58O10Na: 890.022, Found: 889.839.
Compound 6a:
[α]D(CHCl3, c 1.8) = +54.2; 1H NMR (200.13 MHz, CDCl3): δ 3.44(s, 3H), 3.56-3.74(m, 3H), 3.92-4.03(m, 2H), 4.15-4.35(m, 3H), 4.40-4.60(m, 2H), 4.53(ABq, 2H, J = 11.8Hz), 4.59(ABq, 2H, J = 11.9Hz), 5.12(d, 1H, J = 1.3Hz), 5.23-5.31(m, 1H), 5.24(s, 1H), 5.68(t, 1H, J = 9.8Hz), 6.12(t, 1H, J = 9.5Hz), 7.20-7.55(m, 24H), 7.86-8.01(m, 6H) ; 13C NMR (55.32 MHz, CDCl3): δ 55.6, 65.3, 68.3, 68.8, 69.8, 70.7, 72.1, 72.4, 73.0, 73.2, 77.9, 78.1, 81.7, 97.1, 104.6, 127.3129.9, 133.0, 133.2, 133.3, 137.9, 138.1, 138.3, 165.0, 165.8, 165.8 ; Mol. Wt. calculated for C54H52O13Na: 931.973, Found: 931.904.
Compound 6b:
[α]D(CHCl3, c 1.3) = +27.2; 1H NMR (200.13 MHz, CDCl3): δ 1.64(m, 2H), 2.18(m, 2H), 3.41(dd, 1H, J = 6.6, 16.1Hz), 3.66-3.80(m, 3H), 3.90(dd, 1H, J = 2.6, 4.6Hz), 4.10(t, 1H, J = 4.9Hz), 4.35(m, 1H), 4.55(ABq, 2H, J = 12.0Hz), 4.61(ABq, 2H, J = 12.0Hz), 4.62(d, 2H, J = 2.5Hz), 4.91-5.06(m, 2H), 5.10(d, 1H, J = 2.5Hz), 5.80(m, 1H), 7.22-7.40(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 28.7, 30.2, 67.6, 70.0, 72.4, 73.2, 73.4, 77.9, 78.1, 82.5, 105.2, 114.8, 127.5-128.3, 137.8, 138.1, 138.1, 138.2; Mol. Wt. calculated for C31H36O5Na: 511.604, Found: 511.550.
Compound 6c:
[α]D(CHCl3, c 1.3) = +1.2; 1H NMR (200.13 MHz, CDCl3): δ 0.76(d, 3H, J = 6.9Hz), 0.86, 0.87, 0.89, 0.90(4s, 6H), 0.80-1.00(m, 2H), 1.10-1.35(m, 3H), 1.51-1.70(m, 2H), 2.00-2.20(m, 2H), 3.31(dt, 1H, J = 4.27, 10.5Hz), 3.76(dd, 1H, J = 6.8, 10.0Hz), 3.79(dd, 1H, J = 5.2, 10.1Hz), 3.89(dd, 1H, J = 2.7, 4.5Hz), 4.19(t, 1H, J = 5.0Hz), 4.38(dd, 1H J = 5.3, 12.0Hz), 4.56(ABq, 2H, 11.9Hz), 4.60(ABq, 2H, J = 11.9Hz), 4.60(s, 2H), 5.18(d, 1H, J = 2.5Hz), 7.22-7.40(m, 15H) ; 13C NMR (55.32 MHz, CDCl3): δ 16.2, 21.1, 21.2, 23.1, 25.5, 31.5, 34.3, 43.1, 48.5, 69.6, 72.5,
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Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011
73.2, 73.3, 77.6, 77.9, 79.8, 82.6, 106.5, 127.5-128.3, 137.8, 138.1, 138.3; Mol. Wt. calculated for C36H46O5Na: 581.737, Found: 581.426.
Compound 6d:
[α]D(CHCl3, c 1.2) = +28.1; 1H NMR (200.13 MHz, CDCl3): δ 3.34(s, 3H), 3.41-3.75(m, 6H), 3.96(dd, 1H, J = 2.4, 4.5Hz), 4.07(dd, 1H, J = 3.2, 10.8Hz), 4.21(dd, 1H, J = 4.5, 5.8Hz), 4.33(dd, 1H, J = 5.8, 11.5Hz), 4.46-4.86(m, 12H), 4.9(ABq, 2H, J = 10.9Hz), 5.21(d, 1H, J = 1.9Hz), 7.24-7.38(m, 30H) ; 13C NMR (55.32 MHz, CDCl3): δ 55.1, 66.3, 69.7, 69.9, 72.3, 73.2, 73.2, 73.3, 75.1, 75.8, 77.2, 77.8, 77.9, 78.2, 79.8, 82.0, 98.0, 105.4, 127.4-128.4, 137.9, 137.9, 138.1, 138.1, 138.2, 138.7 ; Mol. Wt. calculated for C54H58O10Na: 890.022, Found: 889.905.
Compound 6e:
[α]D(CHCl3, c 1.3) = +48.1; 1H NMR (200.13 MHz, CDCl3): δ 3.70-3.85(m, 4H), 3.93(dd, 1H, J = 2.1, 11.6Hz), 4.05(dd, 1H, J = 5.1, 9.9Hz), 4.18-4.37(m, 4H), 4.46(dd, 2H, J = 2.4, 11.8Hz), 4.54-4.63(m, 4H), 4.79(s, 2H), 5.12(s, 2H), 5.14(d, 1H, J = 2.4Hz), 5.34(d, 1H, J = 8.1Hz), 6.00(d, 1H, J = 1.4Hz), 7.16-7.38(m, 30H), 7.50-7.55(m, 2H), 7.64(d, 1H, J = 8.3Hz); 13C NMR (55.32 MHz, CDCl3): δ 44.0, 65.7, 69.3, 71.2, 72.2, 72.5, 73.3, 73.4, 74.4, 78.2, 78.6, 81.0, 82.2, 89.1, 101.1, 105.1, 127.56-128.67, 129.2, 136.7, 137.1, 137.1, 137.1, 137.2, 137.6, 137.9, 150.6, 162.4 ; Mol. Wt. calculated for C56H56N2O10Na: 940.041, Found: 939.896.
Compound 7:
[α]D(CHCl3, c 1.7) = +13.7; 1H NMR (200.13 MHz, CDCl3): δ 3.28(s, 3H), 3.49(dd, 1H, J = 5.6, 10.6Hz), 3.60(dd, 1H, J = 3.7, 10.5Hz), 3.83(d, 1H, J = 4.5Hz), 4.02(d, 1H, J = 4.8Hz), 4.35(dd, 1H, J = 3.9, 5.9Hz), 4.46(ABq, 2H, J = 11.9Hz), 4.53(d, 2H, J = 1.7Hz), 4.60(dd, 2H, J = 12.0, 16.8Hz), 4.92(s, 1H), 7.15-7.38(m, 15H) ; 13C NMR (55.32 MHz, CDCl3): δ 54.7, 71.0, 72.0, 72.1, 72.8, 78.1, 79.4, 80.2, 106.1, 127.2-128.1, 137.6, 137.6, 138.1; Mol. Wt. calculated for C27H30O5Na: 457.514, Found: 457.426.
Compound 8:
[α]D(CHCl3, c 1.6) = -17.7; 1H NMR (200.13 MHz, CDCl3): δ 3.39(s, 3H), 3.71(dd, 1H, J = 6.9, 10.2Hz), 3.79(dd, 1H, J = 5.0, 10.2Hz), 3.97(dd, 1H, J = 1.4, 2.5Hz), 4.05(dd, 1H, J = 2.5, 5.8Hz), 4.42(m, 1H), 4.49(d, 2H, J = 2.5Hz), 4.52(ABq, 2H J = 10.7Hz), 4.55(dd, 2H, J = 6.6, 12.3Hz), 4.92(d, 1H, J = 1.4Hz), 7.21-7.38(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 55.6, 69.6, 71.8, 72.1, 73.3, 80.0, 81.4, 86.7, 108.0, 127.5-128.4, 137.4, 137.7, 138.2; Mol. Wt. calculated for C27H30O5Na: 457.514, Found: 457.495.
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Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011
Compound 9: [α]D(CHCl3, c 1.3) = +53.3; 1H NMR (200.13 MHz, CDCl3): δ 3.39(s, 3H), 3.60(d, 1H, J = 0.6Hz), 3.61(s, 1H), 3.90(dd, 1H, J = 2.6, 6.2Hz), 3.99(d, 1H, J = 1.9Hz), 4.22(dd, 1H, J = 4.9, 10.6Hz), 4.50(ABq, 2H, J = 11.9Hz), 4.53(Abq, 2H, J = 12.7Hz), 4.53(d, 2H, J = 10.6Hz), 4.96(s, 1H), 7.16-7.41(m, 15H) ; 13C NMR (55.32 MHz, CDCl3): δ 54.9, 69.8, 71.8, 72.0, 73.3, 80.8, 83.4, 88.0, 107.2, 127.5-128.3, 137.5, 17.8, 138.0; Mol. Wt. calculated for C27H30O5Na: 457.514, Found: 457.426. Compound 10: [α]D(CHCl3, c 1.2) = +16.9; 1H NMR (200.13 MHz, CDCl3): δ 3.37(s, 3H), 3.75(d, 1H, J = 0.6Hz), 3.78(s, 1H), 3.89(dd, 1H, J = 2.4, 4.5Hz), 4.19(m, 1H), 4.36(dd, 1H, J = 5.5, 11.9Hz), 4.58(ABq, 2H, J = 12.1Hz), 4.59(ABq, 2H, J = 12.0Hz), 4.60(s, 2H), 5.02(d, 1H, J = 1.5Hz), 7.20-7.38(m, 15H); 13C NMR (55.32 MHz, CDCl3): δ 55.5, 69.6, 72.5, 73.2, 73.4, 77.8, 78.2, 82.4, 106.3, 127.5-128.3, 137.8, 138.0, 138.2; Mol. Wt. calculated for C27H30O5Na: 457.51, Found: 457.495.
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Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011

1H NMR Spectrum (200.13 MHz, CDCl3) of Compound 1a

7.29

0.8

0.7

0.6

0.5

4.61 4.52 4.50
4.37 4.43 4.16
4.08 4.15
3.91

7.34 7.31

0.4

0.3

4.65

5.21

0.2

2.38 2.37
2.36

3.49

3.52

3.59

3.60

3.89

4.71

7.37

7.16

0.1

0.0

19.42

0.90

8.88 3.11

2.41

0.71

10

9

8

7

6

5

4

3

2

1

0

13C NMR Spectrum (50.32MHz, CDCl3) of Compound 1a

127.39 127.71

128.21

1.0

128.27

0.9

0.8

0.7

0.6

0.5

Chloroform-d

138.06 137.57
127.23 103.01
80.54 79.36 77.95
72.93 72.16 70.64 53.87

0.4

0.3

0.2

0.1

0.0

150

100

50

0

DEPT NMR Spectrum (50.32MHz, CDCl3) of Compound1a

1.0

128.22 127.73
127.41 103.01 80.56 79.36 77.94

0.5

0.0

53.88
70.65 72.17 72.31 72.94

-0.5

150

100

50

0
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