Supporting Information for:

Synthesis of Sialic Acids via Desymmetrization

by Ring-Closing Metathesis

Eric A. Voight, Christian Rein, and Steven D. Burke*

Department of Chemistry, University of Wisconsin-Madison,

1101 University Avenue, Madison, WI 53706-1396

*To whom all correspondence should be sent. Phone: (608) 262-4941. Fax: (608) 265-
4534. E-mail: burke@chem.wisc.edu.

Table of Contents:

-Expanded General Methods . . . S2-S3

-X-Ray Data for Compound 38 . . . S4-S14

-Characterization Data Comparison . . . S15-S16

-1H and 13C NMR spectra . . . S17-S44

S1
 Expanded General Methods
Optical rotations were measured on a Perkin-Elmer 241 digital polarimeter.

Concentrations (c) are reported in g/100 mL. Infrared spectra (IR) were obtained on a

Matteson Polaris FT-IR equipped with a DTGS detector. Proton nuclear magnetic resonance

(1H NMR) spectra were recorded on a Bruker AC-300 (300 MHz). Proton NMR splitting

patterns are designated as singlet (s), doublet (d), triplet (t), quartet (q), quintet (quin), sextet

(sex), septet (sept), ab quartet (ABq), multiplet (m), apparent (app), and broad (br). Spectra

were interpreted assuming first-order behavior, and coupling constants were rounded to the

nearest 0.5 hertz (Hz). All expansions were calibrated to 10 Hz/cm. Carbon nuclear

magnetic resonance (13C NMR) spectra were recorded on a Bruker AC-300 (75 MHz).

Carbon resonances were assigned using Distortionless Enhancement by Polarization Transfer

(DEPT) spectra obtained with a phase angle of 90: (C) not observed, (CH) positive, (CH2)

suppressed, (CH3) suppressed or not observed; and with a phase angle of 135: (C) not

observed; (CH) positive; (CH2) negative; (CH3) positive. High resolution mass spectra

(HRMS) using electron impact (EI, 70 eV) were recorded on a Kratos MS-80RFA mass

spectrometer (DS-55/DS-90 peak matching option). High resolution fast atom bombardment

(FAB) mass spectra were obtained on VG Analytical ZAB-2F (Ion Tech FAB gun, 8 kV, Xe

carrier gas).

All moisture-sensitive reactions were performed in flame-dried and/or oven dried

glassware under a positive pressure of nitrogen unless otherwise noted. "Concentrated"

refers to the removal of volatile solvents via distillation using a Bchi rotary evaporator at

water aspirator pressure, followed by residual solvent removal at high vacuum. "Dried"

S2
refers to addition of ~1g/mmol anhydrous sodium or magnesium sulfate followed by

filtration.

Analytical thin layer chromatography (TLC) was carried out on E. Merck

(Darmstadt) TLC plates precoated with silia gel 60 F254 (0.25 mm layer thickness).

Visualization was accomplished using UV light and/or a p-anisaldehyde (PAA) charring

solution. Flash column chromatography (FCC) was performed on EM Science silica gel 60

(230-400 mesh). Solvent mixtures for TLC and FCC are reported in either v1:v2 ratios or

V1/Vtotal x 100%. For columns using MeOH-containing eluents, the column was slurry

packed in MeOH, washed with 2 column volumes (c.v.) of the same, then 2 c.v. of the first

eluent.

Immediately prior to use, toluene (PhCH3) was distilled from sodium naphthalide;

benzene (PhH) and tetrahydrofuran (THF) were distilled from sodium benzophenone ketyl;

methanol (MeOH) was distilled from magnesium methoxide; and dichloromethane (CH2Cl2),

hexanes, dimethylformamide (DMF), and triethylamine (Et3N) were distilled from calcium

hydride. Para-toluenesulfonyl chloride (TsCl) was dissolved in ether (Et2O), washed with

10% sodium hydroxide (NaOH) until clear, dried (MgSO4), and recrystallized (Et2O).

Aluminum trichloride (AlCl3) potassium tert-butoxide (KOtBu), 18-crown-6 (18-c-6),

Grubbs' catalyst, and cesium acetate (CsOAc) were stored, weighed, and sealed from

atmospheric moisture in a dry box prior to use. 1,3-Dichlorotetraisopropyldisiloxane

(TIPSCl2) was distilled under aspirator vacuum. Amberlite IR-120(plus) was washed with

MeOH prior to use. All other reagents and solvents were used as supplied, assuming reagent

purity designated by supplier.

S3
 X-ray Data for Compound 38
OMe
OMe
OMe S
OMe N N
OH N N
O
5 O =
HO 8 O
4 8 Et 3N, THF O S
OH O
O 62% O H
OH H O
36 S 38

S4
Experimental
A colorless prism-shaped crystal of dimensions 0.43 x 0.38 x 0.20 mm was selected for
structural analysis. Intensity data for this compound were collected using a Bruker SMART
ccd area detector(1) mounted on a Bruker P4 goniometer using graphite-monochromated Mo
K radiation ( = 0.71073 ). The sample was cooled to 173(2) K. The intensity data,
which nominally covered one and a half hemispheres of reciprocal space, were measured as a
series of oscillation frames each of 0.4 for 20 sec / frame. The detector was operated in
512 x 512 mode and was positioned 5.00 cm from the sample. Coverage of unique data was
99.2 % complete to 25.00 degrees in . Cell parameters were determined from a non-linear
least squares fit of 3995 peaks in the range 2.58 < < 28.89. The first 50 frames were
repeated at the end of data collection and yielded 181 peaks showing a variation of -0.44 %
during the data collection. A total of 4672 data were measured in the range 2.59 < <
29.20. The data were corrected for absorption by the empirical method (2) giving minimum
and maximum transmission factors of 0.8694 and 0.9361. The data were merged to form a
set of 3712 independent data with R(int) = 0.0181.
The monoclinic space group P2(1) was determined by systematic absences and statistical
tests and verified by subsequent refinement. The structure was solved by direct methods and
refined by full-matrix least-squares methods on F2 (3). Hydrogen atom positions were
initially determined by geometry and were refined using a riding model. Non-hydrogen
atoms were refined with anisotropic displacement parameters. A total of 255 parameters
were refined against 1 restraints and 3712 data to give wR(F2) = 0.0903 and S = 1.034 for
weights of w = 1/[2 (F2) + (0.0640 P)2], where P = [Fo2 + 2Fc2] / 3. The final R(F) was
0.0328 for the 3499 observed, [F > 4(F)], data. The largest shift/s.u. was 0.000 in the final
refinement cycle. The final difference map had maxima and minima of 0.361 and -0.251
e/ 3 , respectively. The absolute structure was determined by refinement of the Flack
parameter(4). The polar axis restraints were taken from Flack and Schwarzenbach(5).

S5
Comment
The displacement ellipsoids were drawn at the 50% probability level.

Acknowledgment
The authors thank the National Science Foundation (grant CHE-9709005) and the University
of Wisconsin for funds to purchase the diffractometer and computers.
This structure was determined by Michael Kavana.

References
(1) (a) Data Collection: SMART Software Reference Manual (1994). Bruker-AXS, 6300
Enterprise Dr., Madison, WI 53719-1173, USA. (b) Data Reduction: SAINT Software
Reference Manual (1995). Bruker-AXS, 6300 Enterprise Dr., Madison, WI 53719-1173,
USA.

(2) G. M. Sheldrick (1996). SADABS. Program for Empirical Absorption Correction of

Area Detector Data. University of Gttingen, Germany.

(3) (a) G. M. Sheldrick (1994). SHELXTL Version 5 Reference Manual. Bruker-AXS, 6300
Enterprise Dr., Madison, WI 53719-1173, USA. (b) International Tables for
Crystallography, Vol C, Tables 6.1.1.4, 4.2.6.8, and 4.2.4.2, Kluwer: Boston (1995).

(4) H. D. Flack, Acta Cryst. A39, 876-881 (1983).

(5) H. D. Flack and D. Schwarzenbach, Acta Cryst. A44, 499-506 (1988).

S6
Table 1. Crystal data and structure refinement for 00115.

Identification code 00115

Empirical formula C18 H18 O8 S2
Formula weight 426.44
Crystal system Monoclinic
Space group P2(1)
Unit cell dimensions a = 6.2079(6) = 90
b = 8.9567(8) = 91.385(2)
c = 16.5736(15) = 90
Volume 921.26(15) 3
Z 2
Density (calculated) 1.537 Mg/m3
Wavelength 0.71073
Temperature 173(2) K
F(000) 444
Absorption coefficient 0.335 mm-1
Absorption correction Empirical
Max. and min. transmission 0.9361 and 0.8694
Theta range for data collection 2.59 to 29.20.
Reflections collected 4672
Independent reflections 3712 [R(int) = 0.0181]
Data / restraints / parameters 3712 / 1 / 255
wR(F2 all data) wR = 0.0903
R(F obsd data) R = 0.0328
Goodness-of-fit on F2 1.034
Observed data [I > 2(I)] 3499
Absolute structure parameter 0.07(6)
Largest and mean shift / s.u. 0.000and 0.000
Largest diff. peak and hole 0.361 and -0.251 e/3

S7
 Table 2. Atomic coordinates and equivalent isotropic displacement parameters
for 00115. U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor.
______________________________________________________________
x y z U(eq)
______________________________________________________________

O(1) 0.7354(2) 0.48364(18) 0.26832(7) 0.0212(3)

C(2) 0.5103(3) 0.5192(2) 0.27045(11) 0.0198(4)
C(3) 0.4863(3) 0.6886(2) 0.26721(12) 0.0211(4)
C(4) 0.5856(3) 0.7505(2) 0.18959(12) 0.0227(4)
C(5) 0.7788(3) 0.6628(2) 0.16023(12) 0.0230(4)
C(6) 0.7826(3) 0.4993(3) 0.18452(10) 0.0217(4)
C(7) 0.5920(4) 0.4186(3) 0.14500(11) 0.0243(4)
C(8) 0.6150(4) 0.2494(3) 0.14599(12) 0.0250(4)
C(9) 0.4251(4) 0.1660(3) 0.10617(15) 0.0332(5)
O(10) 0.5310(3) 0.05711(19) 0.05533(9) 0.0316(4)
O(11) 0.7944(3) 0.20655(18) 0.09496(9) 0.0297(4)
O(12) 0.9591(2) 0.74108(19) 0.19990(9) 0.0267(3)
O(13) 0.6831(2) 0.89626(17) 0.20716(8) 0.0246(3)
O(14) 0.4172(2) 0.45491(17) 0.19709(8) 0.0240(3)
C(15) 0.4143(3) 0.4507(2) 0.34438(11) 0.0198(4)
C(16) 0.5142(3) 0.4791(2) 0.41992(11) 0.0201(4)
C(17) 0.4276(3) 0.4228(2) 0.48952(11) 0.0198(4)
C(18) 0.2377(3) 0.3391(2) 0.48609(12) 0.0207(4)
C(19) 0.1347(3) 0.3139(2) 0.41158(13) 0.0241(4)
C(20) 0.2249(3) 0.3696(2) 0.34153(12) 0.0236(4)
O(21) 0.5354(2) 0.44639(18) 0.56260(8) 0.0241(3)
O(22) 0.1666(2) 0.28820(18) 0.55887(9) 0.0260(3)
C(23) 0.4332(4) 0.5550(3) 0.61261(12) 0.0273(5)
C(24) -0.0349(4) 0.2113(3) 0.55845(16) 0.0346(5)
C(25) 0.8957(4) 0.8780(3) 0.21993(12) 0.0247(4)
C(26) 0.7403(4) 0.0877(3) 0.05169(12) 0.0275(4)
S(27) 1.05442(9) 1.00717(7) 0.25657(3) 0.03144(14)
S(28) 0.91030(11) -0.01363(8) 0.00110(4) 0.03970(16)
______________________________________________________________

S8
Table 3. Bond lengths [] and angles [] for 00115.
______________________________________________________________

O(1)-C(6) 1.433(2) O(10)-C(26) 1.331(3)

O(1)-C(2) 1.435(2) O(11)-C(26) 1.322(3)
C(2)-O(14) 1.452(2) O(12)-C(25) 1.332(3)
C(2)-C(15) 1.506(3) O(13)-C(25) 1.342(3)
C(2)-C(3) 1.525(3) C(15)-C(20) 1.382(3)
C(3)-C(4) 1.543(3) C(15)-C(16) 1.407(3)
C(4)-O(13) 1.466(3) C(16)-C(17) 1.380(3)
C(4)-C(5) 1.523(3) C(17)-O(21) 1.386(2)
C(5)-O(12) 1.463(3) C(17)-C(18) 1.397(3)
C(5)-C(6) 1.519(3) C(18)-O(22) 1.372(2)
C(6)-C(7) 1.521(3) C(18)-C(19) 1.395(3)
C(7)-O(14) 1.440(2) C(19)-C(20) 1.393(3)
C(7)-C(8) 1.523(3) O(21)-C(23) 1.436(3)
C(8)-O(11) 1.466(2) O(22)-C(24) 1.428(3)
C(8)-C(9) 1.531(3) C(25)-S(27) 1.628(2)
C(9)-O(10) 1.457(3) C(26)-S(28) 1.638(2)

C(6)-O(1)-C(2) 102.95(14) O(11)-C(8)-C(9) 102.22(17)

O(1)-C(2)-O(14) 105.04(14) C(7)-C(8)-C(9) 114.17(19)
O(1)-C(2)-C(15) 109.54(15) O(10)-C(9)-C(8) 102.82(18)
O(14)-C(2)-C(15) 111.23(16) C(26)-O(10)-C(9) 110.07(18)
O(1)-C(2)-C(3) 108.31(17) C(26)-O(11)-C(8) 109.71(17)
O(14)-C(2)-C(3) 109.17(16) C(25)-O(12)-C(5) 109.01(17)
C(15)-C(2)-C(3) 113.20(16) C(25)-O(13)-C(4) 108.82(16)
C(2)-C(3)-C(4) 110.26(16) C(7)-O(14)-C(2) 107.53(14)
O(13)-C(4)-C(5) 101.40(16) C(20)-C(15)-C(16) 118.80(17)
O(13)-C(4)-C(3) 109.03(16) C(20)-C(15)-C(2) 122.65(17)
C(5)-C(4)-C(3) 114.49(17) C(16)-C(15)-C(2) 118.40(17)
O(12)-C(5)-C(6) 109.63(17) C(17)-C(16)-C(15) 120.38(18)
O(12)-C(5)-C(4) 102.08(16) C(16)-C(17)-O(21) 119.04(17)
C(6)-C(5)-C(4) 114.80(17) C(16)-C(17)-C(18) 120.50(18)
O(1)-C(6)-C(5) 110.43(16) O(21)-C(17)-C(18) 120.43(17)
O(1)-C(6)-C(7) 101.29(15) O(22)-C(18)-C(19) 125.02(19)
C(5)-C(6)-C(7) 109.70(17) O(22)-C(18)-C(17) 115.58(18)
O(14)-C(7)-C(6) 102.94(15) C(19)-C(18)-C(17) 119.41(18)
O(14)-C(7)-C(8) 106.86(17) C(20)-C(19)-C(18) 119.65(19)
C(6)-C(7)-C(8) 113.37(18) C(15)-C(20)-C(19) 121.23(18)
O(11)-C(8)-C(7) 109.06(17) C(17)-O(21)-C(23) 113.40(16)

S9
C(18)-O(22)-C(24) 117.16(18) O(11)-C(26)-O(10) 112.13(19)
O(12)-C(25)-O(13) 111.62(19) O(11)-C(26)-S(28) 124.44(18)
O(12)-C(25)-S(27) 124.60(17) O(10)-C(26)-S(28) 123.42(17)
O(13)-C(25)-S(27) 123.78(17)
______________________________________________________________

S10
 Table 4. Anisotropic displacement parameters (2x 103 ) for 00115. The
anisotropic displacement factor exponent takes the form:
-2 2[ h2 a*2 U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________________________

O(1) 22(1) 24(1) 18(1) 0(1) 1(1) 5(1)

C(2) 21(1) 19(1) 19(1) -2(1) -2(1) 2(1)
C(3) 24(1) 17(1) 23(1) 1(1) 2(1) 2(1)
C(4) 26(1) 19(1) 24(1) 1(1) -2(1) 0(1)
C(5) 28(1) 22(1) 19(1) -1(1) 2(1) 1(1)
C(6) 30(1) 18(1) 18(1) -1(1) 3(1) 5(1)
C(7) 33(1) 23(1) 17(1) -1(1) 2(1) 3(1)
C(8) 33(1) 20(1) 22(1) -4(1) 5(1) 1(1)
C(9) 38(1) 26(1) 36(1) -8(1) 7(1) -2(1)
O(10) 34(1) 29(1) 32(1) -10(1) 5(1) -4(1)
O(11) 32(1) 23(1) 34(1) -9(1) 7(1) -3(1)
O(12) 26(1) 22(1) 32(1) -4(1) 2(1) 0(1)
O(13) 26(1) 19(1) 29(1) 1(1) 0(1) -1(1)
O(14) 25(1) 26(1) 21(1) -5(1) -3(1) 1(1)
C(15) 22(1) 16(1) 21(1) -1(1) 0(1) 3(1)
C(16) 21(1) 17(1) 23(1) -1(1) 0(1) -2(1)
C(17) 19(1) 18(1) 22(1) -1(1) -1(1) 3(1)
C(18) 22(1) 14(1) 27(1) 2(1) 5(1) 1(1)
C(19) 21(1) 19(1) 32(1) -2(1) -1(1) -1(1)
C(20) 24(1) 19(1) 28(1) -2(1) -5(1) -1(1)
O(21) 24(1) 29(1) 20(1) -1(1) -1(1) 1(1)
O(22) 26(1) 23(1) 29(1) 5(1) 6(1) -2(1)
C(23) 34(1) 27(1) 21(1) -2(1) 3(1) -4(1)
C(24) 27(1) 36(1) 41(1) 9(1) 6(1) -8(1)
C(25) 28(1) 23(1) 23(1) 3(1) 2(1) -1(1)
C(26) 35(1) 26(1) 22(1) -1(1) 4(1) -3(1)
S(27) 32(1) 28(1) 35(1) -4(1) 4(1) -9(1)
S(28) 46(1) 37(1) 37(1) -13(1) 15(1) -2(1)
______________________________________________________________

S11
Table 5. Hydrogen coordinates and isotropic displacement parameters for
00115.
______________________________________________________________
x y z U(eq)
______________________________________________________________

H(3A) 0.5595 0.7337 0.3150 0.025

H(3B) 0.3317 0.7155 0.2684 0.025
H(4) 0.4731 0.7595 0.1456 0.027
H(5) 0.7887 0.6721 0.1003 0.028
H(6) 0.9224 0.4508 0.1713 0.026
H(7) 0.5631 0.4562 0.0890 0.029
H(8) 0.6407 0.2129 0.2024 0.030
H(9A) 0.3360 0.1163 0.1470 0.040
H(9B) 0.3330 0.2345 0.0735 0.040
H(16) 0.6419 0.5374 0.4230 0.024
H(19) 0.0038 0.2590 0.4086 0.029
H(20) 0.1548 0.3515 0.2909 0.028
H(23A) 0.5172 0.5670 0.6630 0.041
H(23B) 0.2874 0.5213 0.6248 0.041
H(23C) 0.4254 0.6508 0.5842 0.041
H(24A) -0.0616 0.1727 0.6126 0.052
H(24B) -0.0308 0.1281 0.5201 0.052
H(24C) -0.1506 0.2804 0.5423 0.052
______________________________________________________________

S12
Table 6. Torsion angles [] for 00115.
______________________________________________________________

C(6)-O(1)-C(2)-O(14) 37.8(2) C(6)-C(7)-O(14)-C(2) -12.9(2)

C(6)-O(1)-C(2)-C(15) 157.32(16) C(8)-C(7)-O(14)-C(2) 106.75(18)
C(6)-O(1)-C(2)-C(3) -78.79(18) O(1)-C(2)-O(14)-C(7) -14.5(2)
O(1)-C(2)-C(3)-C(4) 59.0(2) C(15)-C(2)-O(14)-C(7) -132.92(17)
O(14)-C(2)-C(3)-C(4) -54.8(2) C(3)-C(2)-O(14)-C(7) 101.46(18)
C(15)-C(2)-C(3)-C(4) -179.32(16) O(1)-C(2)-C(15)-C(20) -132.0(2)
C(2)-C(3)-C(4)-O(13) -145.03(17) O(14)-C(2)-C(15)-C(20) -16.3(3)
C(2)-C(3)-C(4)-C(5) -32.3(2) C(3)-C(2)-C(15)-C(20) 107.0(2)
O(13)-C(4)-C(5)-O(12) 25.46(18) O(1)-C(2)-C(15)-C(16) 52.4(2)
C(3)-C(4)-C(5)-O(12) -91.76(19) O(14)-C(2)-C(15)-C(16) 168.10(17)
O(13)-C(4)-C(5)-C(6) 143.98(16) C(3)-C(2)-C(15)-C(16) -68.6(2)
C(3)-C(4)-C(5)-C(6) 26.8(2) C(20)-C(15)-C(16)-C(17) 2.0(3)
C(2)-O(1)-C(6)-C(5) 71.19(19) C(2)-C(15)-C(16)-C(17) 177.79(18)
C(2)-O(1)-C(6)-C(7) -45.0(2) C(15)-C(16)-C(17)-O(21)
O(12)-C(5)-C(6)-O(1) 67.8(2) 176.80(18)
C(4)-C(5)-C(6)-O(1) -46.4(2) C(15)-C(16)-C(17)-C(18) -1.1(3)
O(12)-C(5)-C(6)-C(7) 178.58(14) C(16)-C(17)-C(18)-O(22)
C(4)-C(5)-C(6)-C(7) 64.4(2) 179.77(18)
O(1)-C(6)-C(7)-O(14) 35.58(19) O(21)-C(17)-C(18)-O(22) 1.9(3)
C(5)-C(6)-C(7)-O(14) -81.13(17) C(16)-C(17)-C(18)-C(19) -0.6(3)
O(1)-C(6)-C(7)-C(8) -79.48(19) O(21)-C(17)-C(18)-C(19)-
C(5)-C(6)-C(7)-C(8) 163.80(16) 178.51(18)
O(14)-C(7)-C(8)-O(11) -178.87(15) O(22)-C(18)-C(19)-C(20)-
C(6)-C(7)-C(8)-O(11) -66.2(2) 179.00(19)
O(14)-C(7)-C(8)-C(9) 67.5(2) C(17)-C(18)-C(19)-C(20) 1.4(3)
C(6)-C(7)-C(8)-C(9) -179.77(17) C(16)-C(15)-C(20)-C(19) -1.2(3)
O(11)-C(8)-C(9)-O(10) 16.0(2) C(2)-C(15)-C(20)-C(19) -176.79(19)
C(7)-C(8)-C(9)-O(10) 133.59(18) C(18)-C(19)-C(20)-C(15) -0.5(3)
C(8)-C(9)-O(10)-C(26) -10.8(2) C(16)-C(17)-O(21)-C(23) 106.6(2)
C(7)-C(8)-O(11)-C(26) -138.15(19) C(18)-C(17)-O(21)-C(23) -75.5(2)
C(9)-C(8)-O(11)-C(26) -17.0(2) C(19)-C(18)-O(22)-C(24) -3.9(3)
C(6)-C(5)-O(12)-C(25) -143.39(16) C(17)-C(18)-O(22)-C(24) 175.7(2)
C(4)-C(5)-O(12)-C(25) -21.3(2) C(5)-O(12)-C(25)-O(13) 7.6(2)
C(5)-C(4)-O(13)-C(25) -22.74(19) C(5)-O(12)-C(25)-S(27) -173.18(15)
C(3)-C(4)-O(13)-C(25) 98.39(19) C(4)-O(13)-C(25)-O(12) 10.5(2)

S13
C(4)-O(13)-C(25)-S(27) -168.75(15)
C(8)-O(11)-C(26)-O(10) 11.2(2)
C(8)-O(11)-C(26)-S(28) -167.32(16)
C(9)-O(10)-C(26)-O(11) 0.3(3)
C(9)-O(10)-C(26)-S(28) 178.85(17)

S14
 Characterization Data Comparison
-KDN derivative 42
Ref. Optical Rotation Infrared M. P.

1 [ ]24D -6.3 1751, 1373, 117-119 C

(c = 0.13; CHCl 3) 1244, 1058
24
2 [ ] D -6.5 not reported "syrup"
(c = 1; CHCl 3 )

3 [ ]
24
D -6.8 1748, 1373, 115-116 C
1220, 1050
(c = 0.28; CHCl 3)

1
H NMR Comparison: Chemical Shifts and Coupling Constants

e = experimental
1
o = Ogura et al.
2
-OAc: m = Mononen et al.
e = 2.12, 2.08, 2.04, 2.02, 2.00 e = 4.06, 10, 2 e = 5.32, 11.5, 10, 5
o = 1.97-2.12 o = 4.05, 10, 2.2 o = 5.30, 11.4, 10, 5.3
m = 2.16, 2.12, 2.07, 2.06, 2.03 m = 4.10, 10, 2.2 m = 5.36, 11.7, 10, 5.1
e = 5.31, 6.5, 5.5 e = 3.26
e = 4.15, 12.5, 6.5 o = 5.29, 6.8, 2.2 o = 3.25
o = 4.14, 12.5, 6.8 m = 5.34, 6.6, 5.4 OAc H m = 3.30
m = 4.20, 12.6, 6.6 H OMe
AcO H
AcO
& O CO2Me e = 3.82
e = 4.71, 12.5, 2.5
AcO H o = 3.80
H H m = 3.86
o = 4.70, 12.5, 2.2 H OAc
m = 4.76, 12.6, 2.4 H H
e = 2.52, 13, 5
e = 5.42, 5.5, 2.5 o = 2.51, 13, 5.3
o = 5.40, 5.4, 2.2 e = 4.90, 10, 10 e = 1.84, 13, 11.5 m = 2.56, 12.9, 5.1
m = 5.46, 5.4, 2.2 o = 4.88, 10, 10 o = 1.83, 13, 11.4
m = 4.94, 10, 10 m = 1.88, 12.9, 11.7

(1) Nakamura, M.; Takayanagi, H.; Furuhata, K.; Ogura, H. Chem. Pharm. Bull. 1992, 40, 879-
885.
(2) Mononen, I.; Lengstad, B.; Lnngren, J. Acta Chem. Scand. B 1980, 34, 775-776.
(3) This workobserved values

S15
-Neu5Ac derivative 51

Ref. Optical Rotation tlc R f Infrared M. P.

1 []25 D -12.0 0.25

(EtOAc)
(c = 1.05; CHCl 3)
21
2 [] D -14.7 0.43 (3:2 3400, 1741,
PhH/acetone) 1660, 1540
(c = 1.5; CHCl 3)

3 []21D -19.9 1740, 1665, 134-135 C

1530
(c = 1; CHCl 3 )
22
5 [] D -12 0.25 1745, 1664, 131-133 C
(EtOAc) 1541
(c = 0.67; CHCl 3)

1
H NMR Comparison

Experimental (300 MHz)

Zbiral and coworkers (250 MHz)4

(1) Julina, R.; Mller, I.; Vasella, A. Carbohyd. Res. 1987, 164, 415-432.
(2) Okamoto, K.; Kondo, T.; Goto, T. Bull. Chem. Soc. Jpn. 1987, 60, 631-636.
(3) Ogura, H.; Furuhata, K. Carbohyd. Res. 1986, 158, 37-51.
(4) Zbiral, E.; Brandstetter, H. H. Monatsh. Chem. 1985, 116, 87-98.
(5) This workobserved values

S16
 MeO OMe

O
O

33
Br

5.99

4.01
3.05
0.98 1.02 1.03 1.97
1.00 1.02
0.98 1.03 1.01

7 6 5 4 3 2 1 0 PPM
S17
 MeO OMe

O
O

33
Br

150 100 50 0 PPM

S18
 MeO OMe

O
O

34

6.04
3.04
1.98
0.99 2.03
1.99 2.00
1.00
0.99 1.00 1.02

7 6 5 4 3 2 1 0 PPM
S19
 MeO OMe

O
O

34

150 100 50 0 PPM

S20
 OMe
OMe

O
35

6.05

2.00 2.02 1.02 0.97 1.02

1.00 1.01
1.00 0.98 1.02

7 6 5 4 3 2 1 0 PPM
S21
 OMe
OMe

O
35

150 100 50 0 PPM

S22
 OMe
OMe
OH
O
HO
OH
O
OH
36

5.98

0.97 1.01 1.02 0.99

1.00 1.00 1.03
1.01 1.01 0.99 0.98 1.03

7 6 5 4 3 2 1 0 PPM
S23
 OMe
OMe
OH
O
HO
OH
O
OH
36

150 100 50 0 PPM

S24
 OMe
OMe
OAc
O

OAc
OAc O
OAc
40

7.00

2.99 3.00
1.00 1.01 1.00
0.97 1.01 0.98 2.98 1.00 3.00
0.97 0.99 0.97 1.02

7 6 5 4 3 2 1 0 PPM
S25
 OMe
OMe
OAc
O

OAc
OAc O
OAc
40

150 100 50 0 PPM

S26
 OAc OMe
AcO
O OMe
AcO
AcO OAc
OMe
41

5.99
6.03
2.98
1.00 3.03 3.00 3.00
2.02
1.01 0.97 1.02 1.02 2.99
1.02 0.99

7 6 5 4 3 2 1 0 PPM
S27
 OAc OMe
AcO
O OMe
AcO
AcO OAc
OMe
41

150 100 50 0 PPM

S28
 OAc OMe
AcO
AcO O CO2Me
AcO OAc
42

5.97

2.99
2.02 2.99
0.98 1.01 2.96 2.95
1.00 3.02
0.99
0.99 1.02 1.00

7 6 5 4 3 2 1 0 PPM
S29
 OAc OMe
AcO
AcO O CO2Me
AcO OAc
42

150 100 50 0 PPM

S30
 OMe
OMe
OH
O

OH
OH O
OH
45

5.98

1.00 1.01 1.01 1.03

0.99 1.02 1.00 1.01 1.01
1.00 0.99 1.02

7 6 5 4 3 2 1 0 PPM
S31
 OMe
OMe
OH
O

OH
OH O
OH
45

150 100 50 0 PPM

S32
 OMe
OMe
OH
O
O
OH O Si(iPr) 2
O
46 (iPr)2Si O

28.09

6.03

1.00 0.96 1.98

0.99 0.99 0.99 0.99 1.02
1.02 0.96 1.01

7 6 5 4 3 2 1 0 PPM
S33
 OMe
OM
OH
O
O
OH O Si(iPr) 2
O
46 (iPr)2Si O

150 100 50 0 PPM

S34
 OMe
OMe

O
O
O O
O Si(iPr) 2
47 (iPr) Si O
2

28.13

5.99

2.00
3.06 1.03
0.98
2.01
1.01 1.01 1.00

7 6 5 4 3 2 1 0 PPM
S35
 OMe
OMe

O
O
O O
O Si(iPr) 2
47 (iPr) Si O
2

150 100 50 0 PPM

S36
 OMe
OMe
N3
O
O
OH O Si(iPr) 2
O
48 (iPr) Si O
2

28.04

6.00
2.00 1.00
2.05 2.00
0.98 0.97
1.00 1.00 1.01 0.99

7 6 5 4 3 2 1 0 PPM
S37
 OMe
OMe
N3
O
O
OH O Si(iPr) 2
O
48 (iPr) Si O
2

150 100 50 0 PPM

S38
 OAc OMe
AcO OMe
O
N3
AcO OAc
OMe
49

9.06

6.05
1.99 2.91 2.90
1.03 1.02
1.00 0.97 0.94 1.04 1.05
1.03 0.98 0.98

7 6 5 4 3 2 1 0 PPM
S39
 OAc OMe
AcO OMe
O
N3
AcO OAc
OMe
49

150 100 50 0 PPM

S40
 OAc OMe
AcO
O CO2Me
N3
AcO OAc
50

6.01

3.00
2.97 2.92
2.03
1.00 1.00 1.00 0.99 0.99 1.03 3.04 1.00

7 6 5 4 3 2 1 0 PPM
S41
 OAc OMe
AcO
O CO2Me
N3
AcO OAc
50

150 100 50 0 PPM

S42
 OAc OMe
AcO
O CO2Me
AcHN
AcO OAc
51

6.12

3.01 3.06
3.01 3.00
2.04 3.99
1.00 1.00 2.99
1.01 1.03

7 6 5 4 3 2 1 0 PPM
S43
 OAc OMe
AcO
O CO2Me
AcHN
AcO OAc
51

150 100 50 0 PPM

S44