B. Wu, R. Woodward, L. Wen, X. Wang, G. Zhao, P. G. Wang
2.9, J = 10.9 Hz, 1 H), 3.94–3.84 (m, 2 H), 2.30–2.23 (m, 2 H), 25.4, 24.9, 23.2, 22.3, 18.8, 18.8, 17.4, 15.7, 15.7 ppm. 31P NMR
FULL PAPER
2.22–2.11 (m, 13 H), 2.10–2.02 (m, 4 H), 1.85 (s, 3 H), 1.80 (s, 3
(162 MHz, D2O): δ = –9.9, –11.8 ppm. HRMS (ESI): calcd. for
H), 1.75 (s, 3 H), 1.71 (s, 3 H), 1.68 (s, 6 H) ppm. 13C NMR C33H58NO12P2 [M – H]– 722.3440; found 722.3437.
(125 MHz, D2O): δ = 174.7, 160.3, 141.2, 135.8, 134.9, 134.4, 130.6,
Supporting Information (see footnote on the first page of this arti-
124.6, 124.5, 124.3, 121.2, 94.7, 72.2, 68.7, 67.7, 62.7, 61.3, 49.9,
cle): Copies of the 1H and 13C NMR spectra of all new compounds.
48.9, 39.7, 39.7, 32.0, 31.9, 26.7, 26.6, 26.1, 25.4, 23.1, 22.9, 22.3,
17.4, 15.8, 15.7 ppm. 31P NMR (162 MHz, D2O): δ = –10.4,
–13.1 ppm. HRMS (ESI): calcd. for C33H56NO12P2 [M – H]–
Acknowledgments
720.3283; found 720.3276.
The authors thank National Institute of Health (NIH)
(R01 GM085267) for financial support of this work.
GalNAc-PP-(all-Z)-pentaprenyl (34): GalNAc-PP-(all-Z)-pent was
prepared from (all-Z)-pentaprenyl-1-P (46 mg) according to the ge-
neral procedure. Following the deprotection step, the crude product
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was purified by C-18 reverse-phase column chromatography to give
1
GalNAc-PP-(all-Z)-pent (15 mg, 20%) as a white solid. H NMR
(500 MHz, D2O): δ = 5.62 (dd, J = 3.0, J = 6.5 Hz, 1 H), 5.51 (t,
J = 6.0 Hz, 1 H), 5.24–5.12 (m, 4 H), 4.53 (t, J = 6.2 Hz, 2 H),
4.30 (d, J = 11.1 Hz, 1 H), 4.25 (t, J = 5.9 Hz, 1 H), 4.09 (d, J =
2.4 Hz, 1 H), 4.01 (dd, J = 2.6, J = 10.9 Hz, 1 H), 3.88–3.78 (m, 2
H), 2.22–2.00 (m, 19 H), 1.79 (s, 3 H), 1.73 (s, 3 H), 1.72–1.68 (m,
9 H), 1.63 (s, 3 H) ppm. 13C NMR (125 MHz, D2O): δ = 174.7,
141.3, 135.4, 135.4, 134.8, 134.7, 125.2, 125.1, 124.9, 124.4, 124.4,
94.8, 72.2, 68.6, 67.7, 62.8, 61.3, 49.8, 32.1, 32.1, 31.8, 26.6, 26.4,
26.2, 25.5, 25.4, 23.2, 23.2, 23.0, 23.0, 22.3, 17.3, 15.7 ppm. 31P
NMR (162 MHz, D2O): δ = –10.1, –12.3 ppm. HRMS (ESI): calcd.
for C33H56NO12P2 [M – H]– 720.3283; found 720.3265.
GalNAc-PP-solanesyl (35): GalNAc-PP-solan was prepared from
solanesyl-1-P (44 mg) according to the general procedure. However,
the two purification steps were reversed as the final product proved
too insoluble to obtain suitable spectroscopic data. The crude prod-
uct was thus purified by C-18 reverse-phase column chromatog-
raphy to give peracetylated GalNAc-PP-solan (35 mg, 50%) as a
1
white solid. H NMR (500 MHz, CD3OD): δ = 5.61 (dd, J = 3.3,
J = 7.3 Hz, 1 H), 5.43 (t, J = 6.6 Hz, 2 H), 5.22 (dd, J = 3.1, J =
11.3 Hz, 1 H), 5.14–5.04 (m, 8 H), 4.59 (t, J = 7.0 Hz, 1 H), 4.53
(t, J = 6.3 Hz, 3 H), 4.21 (dd, J = 8.2, J = 10.8 Hz, 1 H), 4.04 (dd,
J = 5.8, J = 10.8 Hz, 1 H), 2.11 (s, 3 H), 2.10–2.02 (m, 18 H), 1.99
(s, 3 H), 1.99–1.94 (m, 17 H), 1.90 (s, 3 H), 1.69 (s, 3 H), 1.65 (s, 3
H), 1.59 (s, 3 H), 1.58 (s, 21 H) ppm. 13C NMR (125 MHz,
CD3OD): δ = 174.5, 172.4, 172.2, 171.9, 140.8, 136.3, 135.9, 135.9,
135.9, 135.8, 132.1, 125.7, 125.7, 125.6, 125.4, 122.7, 122.6, 96.5,
70.6, 68.7, 64.0, 64.0, 62.3, 41.0, 41.0, 41.0, 40.9, 40.8, 34.5, 33.2,
30.9, 30.8, 30.7, 30.6, 30.5, 28.0, 27.9, 27.8, 27.7, 27.7, 27.7, 26.0,
24.0, 23.8, 23.0, 20.8, 20.7, 20.7, 17.9, 16.8, 16.2, 15.7, 14.5 ppm.
31P NMR (162 MHz, CD3OD): δ = –9.6, –12.5 ppm. HRMS (ESI):
calcd. for C59H94NO15P2, [M – H]– 1118.6104; found 1118.6112.
Final deprotection with NaOCH3 (0.1% in CH3OH) and filtration
though a short bed of C-18 reverse-phase silica gel gave GalNAc-
PP-solan (31 mg, 99%). HRMS (ESI): calcd. for C53H88NO12P2
[M – H]– 992.5787; found 992.5780.
GalNAc-PP-MS-pentaprenyl (36): GalNAc-PP-MS-pent was pre-
pared from MS-pentaprenyl-1-P (54 mg) according to the general
procedure. Following the deprotection step, the crude product was
purified by C-18 reverse-phase column chromatography to give
1
GalNAc-PP-MS-pent (27 mg, 26 %) as a white solid. H NMR
(500 MHz, D2O): δ = 5.55 (dd, J = 3.3, J = 7.1 Hz, 1 H), 5.22–
5.05 (m, 4 H), 4.26 (dt, J = 2.9, J = 11.0 Hz, 1 H), 4.19 (dd, J =
5.2, J = 7.1 Hz, 1 H), 4.06–3.93 (m, 4 H), 3.84–3.72 (m, 2 H), 2.11–
2.02 (m, 11 H), 2.01–1.92 (m, 6 H), 1.69 (s, 3 H), 1.66 (s, 3 H) 1.61
(s, 3 H), 1.58 (s, 6 H), 1.54–1.24 (m, 4 H), 1.22–1.10 (m, 1 H), 0.92
(d, J = 6.5 Hz, 3 H) ppm. 13C NMR (125 MHz, D2O): δ = 174.7,
135.0, 134.8, 134.5, 130.8, 125.7, 124.4, 124.2, 94.7, 72.1, 68.6, 67.7,
64.9, 61.3, 49.9, 49.8, 39.6, 37.3, 37.1, 31.8, 29.0, 26.6, 26.6, 26.5,
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