References
1a
De Clercq E.
Int. J. Antimicrob. Agents
2001,
18:
309
1b
Herdewijn P.
Balzarini J.
De Clercq E.
Adv.
Antiviral Drug
1993,
1:
233
1c
Huryn DM.
Okabe M.
Chem. Rev.
1992,
92:
1745
1d
Périgaud C.
Gosselin G.
Imbach JL.
Nucleosides Nucleotides
1992,
11:
903
2
Yüntsen H.
Yonehara H.
Ui H.
J.
Antibiot. Ser A
1956,
9:
195
3a
Nakajima M.
Itoi K.
Takamatsu Y.
Kinoshita T.
Okazaki T.
Kawakubo K.
Shindo M.
Honma T.
Tohjigamori M.
Haneishi T.
J. Antibiot.
1991,
44:
293
3b
Haruyama H.
Takayama T.
Kinoshita T.
Kondo M.
Nakajima M.
Haneishi T.
J. Chem. Soc., Perkin Trans.
1
1991,
1637
4
Paquette LA.
Brand S.
Behrens C.
J.
Org. Chem.
1999,
64:
2010
5a
Cappelaci L.
Barboni G.
Palmieri M.
Pasqualini M.
Grifantini M.
Costa B.
Martini C.
Franchetti P.
J.
Med. Chem.
2002,
45:
1196
5b
Kodama T.
Shuto S.
Nomura M.
Matsuda A.
Chem.-Eur. J.
2001,
7:
2332
6
Faivre-Buet V.
Grouiller A.
Descotes G.
Nucleosides Nucleotides
1992,
11:
1411
7
Uteza V.
Chen G.-R.
Le Quan Tuoi J.
Descotes G.
Fenet B.
Grouiller A.
Tetrahedron
1993,
49:
8579
8
Yoshimura Y.
Kano F.
Miyazaki S.
Ashida N.
Sakata S.
Haragushi K.
Itoh Y.
Tanaka H.
Miyasaka T.
Nucleosides
Nucleotides
1996,
15:
305
9a
Itoh Y.
Haraguchi K.
Tanaka H.
Gen E.
Miyasaka T.
J. Org. Chem.
1995,
60:
656
9b
Haraguchi K.
Itoh Y.
Tanaka H.
Yamaguchi K.
Miyasaka T.
Tetrahedron
Lett.
1993,
34:
6913
10
Gimisis T.
Chatgilialoglu C.
J. Org. Chem.
1996,
61:
1908
From d-fructose:
11a
Prisbe EJ.
Smejkal J.
Verheyden JPH.
Moffatt JG.
J.
Org. Chem.
1976,
41:
1836
11b
Grouiller A.
Chattopadhyaya J.
Acta Chem. Scand.
1984,
B38:
367
11c
Bouali A.
Ewing DF.
Mackenzie G.
Nucleosides
Nucleotides
1994,
13:
491
11d From d-fructose via
aminooxazolidine intermediate: Yoshimura Y.
Ueda T.
Matsuda A.
Tetrahedron
Lett.
1991,
32:
4549
11e See also: Yoshimura Y.
Otter BA.
Ueda T.
Matsuda A.
Chem. Pharm.
Bull.
1992,
40:
1761
11f From nitrosugar: Mahmood K.
Vasella A.
Bernet B.
Helv. Chim. Acta
1991,
74:
1555
11g From d-ribonolactone: Hayakawa H.
Miyazawa M.
Tanaka H.
Miyasaka T.
Nucleosides Nucleotides
1994,
13:
297
12a
Bravo F.
Castillón S.
Eur.
J. Org. Chem.
2001,
507
12b
Bravo F.
Díaz Y.
Castillón S.
Tetrahedron: Asymmetry
2001,
12:
1635
13
Danishefsky SJ.
Bilodeau MT.
Angew. Chem., Int.
Ed. Engl.
1996,
35:
1380
14a
Yang WB.
Yang YY.
Gu YF.
Wang SH.
Chang CC.
Lin CH.
J.
Org. Chem.
2002,
67:
3773
14b
Lakhrissi Y.
Taillefumier C.
Lakhrissi M.
Chapleur Y.
Tetrahedron: Asymmetry
2000,
9:
417
14c
Rubinstenn G.
Mallet J.-M.
Sinaӱ P.
Tetrahedron
Lett.
1998,
39:
3697
14d
Johnson CR.
Johns BA.
Synlett
1997,
1406
14e
Gervay J.
Flaherty TM.
Holmes D.
Tetrahedron
1997,
53:
16355
14f
Bandzouzi A.
Chapleur Y.
Carbohydr. Res.
1987,
171:
13
14g
Chapleur Y.
J.
Chem. Soc., Chem. Commun.
1984,
449
15 For the preparation of (S)-enantiomer see: Evans DA.
Ripin DHB.
Halstead DP.
Campos KR.
J. Am. Chem. Soc.
1999,
121:
6816
16
Bartlett PA.
Myerson J.
J. Am. Chem. Soc.
1978,
100:
3950
17
Nicotra F.
Panza L.
Ronchetti F.
Russo G.
Toma L.
Carbohydr.
Res.
1987,
171:
49
18a
Tatibouët A.
Rollin P.
Martin OR.
J. Carbohydr. Chem.
2000,
19:
641
18b
Hirota K.
Takasu H.
Tsuji Y.
Sajiki H.
Chem. Commun.
1999,
1827
18c
Link JT.
Raghavan S.
Gallant M.
Danishefsky SJ.
Chou TC.
Ballas LM.
J.
Am. Chem. Soc.
1996,
118:
2825
19a
Díaz Y.
El-Laghdach A.
Matheu MI.
Castillón S.
J. Org. Chem.
1997,
62:
1501
19b
Díaz Y.
El-Laghdach A.
Castillón S.
Tetrahedron
1997,
53:
10921
20a
McDonald FE.
Gleason MM.
Angew. Chem., Int. Ed. Engl.
1995,
34:
350
20b
Kim CU.
Misco PF.
Tetrahedron
Lett.
1992,
33:
5733
21
Wang J.
Wurster JA.
Wilson LJ.
Liotta D.
Tetrahedron
Lett.
1993,
34:
4881
22a
Robles R.
Izquierdo I.
Rodríguez C.
Plaza MT.
Mota AJ.
Alvarez
de Cienfuegos L.
Tetrahedron: Asymmetry
2002,
13:
399
22b
Noort D.
Veeneman GH.
Boons GPH.
van der Marel GA.
Mulder GJ.
van Boom JH.
Synlett
1990,
205
23
Compound 11: t-BuOK (165 mg, 1.35 mmol) was added
to a solution of 6 (220 mg, 0.52 mmol)
in dry CH2Cl2 (10 mL). The mixture was kept
at r.t. for 2.5 h, poured into 10% Na2S2O3 and
extracted with CH2Cl2. The organic phase was dried
with MgSO4 and concentrated to obtain 9.
To a solution of the previously obtained exo-glycal 9 in CH2Cl2 (2.5
mL) N4-Acetyl-bis(trimethylsilyl)cytosine (0.68 mmol) and
NIS (155 mg, 0.68 mmol) were added, and the reaction was kept at
r.t. for 2 h, diluted with NaHCO3 and extracted with
CH2Cl2. The combined organic layers were dried
with MgSO4 and concentrated. Purification by column chromatography
(Merck silica gel 60, 0.040-0.063 mm, eluent: EtOAc-hexane,
5:3) and radial chromatography (Merck silica gel 60 F254)
gave 11 (40 mg, 14% yield).
1H
NMR (300 MHz, CDCl3): δ (ppm) = 9.79
(s, 1 H, NH), 8.13 (d, 1 H, J
6,5 = 7.5
Hz, H-6), 7.50-7.46, 7.36-7.24 (2 m, 16 H, H-Ar,
H-5), 4.50 (d, 1 H, J
gem = 10.8
Hz, H-1′a), 4.30-4.25 (m, 1 H, H-5′),
3.71 (d, 1 H, H-1′b), 3.30-3.22 (m, 2 H, H-6′),
2.97-2.89, 2.75-2.65 (2 m, 2 H, H-3′),
2.27 (s, 3 H, CH3), 2.00-1.88 (m, 2 H, H-4′).
13C
NMR (75.4 MHz, CDCl3): δ(ppm) = 179.0
(CO), 163.0 (C-2), 145.0 (C-6), 143.5 (C-Arq), 128.5,
127.8, 127.0 (CH-Ar), 98.2 (C-2′), 95.6 (C-5), 86.7 (C-Ph3),
80.5 (C-5′), 65.3 (C-6′), 35.3 (C-3′),
27.8 (C-4′), 24.9 (CH3), 12.1 (C-1′).
24a
Stavber S.
Sotler-Pecan T.
Zupan M.
Tetrahedron Lett.
1994,
35:
1105
24b
Stavber S.
Sotler-Pecan T.
Zupan M.
Bull.
Chem. Soc. Jpn.
1996,
69:
169
25a
Vincent SP.
Burkart MD.
Tsai CY.
Zhang Z.
Wong CH.
J.
Org. Chem.
1999,
64:
5264
25b
Taylor SD.
Kotoris CC.
Hum G.
Tetrahedron
1999,
55:
12431
25c
Albert M.
Dax K.
Ortner J.
Tetrahedron
1998,
54:
4839
25d
Burkart MD.
Zhang Z.
Hung SC.
Wong CH.
J.
Am. Chem. Soc.
1997,
119:
11743
26
Albert M.
Paul B.
Dax K.
Synlett
1999,
1483
27
Dax K.
Albert M.
Ortner J.
Paul BJ.
Curr. Org. Chem.
1999,
3:
287
28
Dax K.
Albert M.
Ortner J.
Paul BJ.
Carbohydr. Res.
2000,
327:
47
29
Compound 13: Following
a similar procedure for the synthesis of 9, exo-glycal 10 was
prepared starting from 8 (290 mg, 0.52
mmol) in dry CH2Cl2 (10 mL) using t-BuOK (176 mg, 1.56 mmol). To a solution
of exo-glycal 10 in CH3NO2 (4
mL) N4-Acetyl-bis(trimethylsilyl)cytosine (1.04 mmol)
was added. Selectfluor {1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane
bis(tetrafluoroborate)} (272 mg, 0.77 mmols) was added
and the reaction was kept at r.t. for 25 min. Then, the mixture
was diluted with EtOAc, filtered and concentrated to dryness. Purification
by radial chromatography (Merck silica gel 60 F254, eluent:
CH2Cl2-CH3OH, 50:1) gave
191 mg (61% yield) of 13 as an inseparable
diastereomeric mixture.
1H NMR (400
MHz, CDCl3) diastereomeric mixture: δ (ppm) = 9.90
(br s, 2 H, NH), 8.27 (d, 1 H, J = 7.6
Hz, H-6a), 8.19 (d, 1 H, J = 8.0
Hz, H-6b), 7.46-7.45 (m, 2 H, H-5a, H-5b), 7.38-7.19,
6.84-6.82 (m, 26 H, H-Ar), 5.03-4.59 (m, 4 H,
H1′a, H1′b), 4.48-4.47, 4.31-4.27
(2 m, 2 H, H5′a, H5′b), 3.89 [s, 6 H,
CH3(DMTr)], 3.35-3.17 (m, 4 H, H6′a,
H6′b), 2.96-2.36 (m, 4 H, H3′a, H3′b),
2.27 [s, 3 H, CH3(OAc)], 2.24 [s,
3 H, CH3(OAc)], 1.93-1.75 (m, 4 H,
H-4′a, H-4′b).
13C
NMR (100.6 MHz, CDCl3): δ (ppm) = 158.5
(C=O), 146.4, 145.0 (C-6), 135.8, 135.6, 135.5, 130.0,
129.9, 128.0, 127.9, 127.7, 126.8 (C-Ar), 113.2, 113.1 (C-2′),
99.2, 96.4 (C-5), 86.3, 86.1 (C-Ph3), 83.1 (J
C,F = 181.3),
83.3 (J
C,F& nbsp;= 179.3)
(C-1′), 80.9 (C-5′), 65.2, 64.1 (C-6′),
55.1 (OCH3), 32.8, 32.2 (C-3′), 27.1, 26.4 (C-4′),
24.8 (CH3).
19F NMR (400
MHz, CDCl3): δ (ppm) = -228.03
(t, J = 48.9 Hz), -228.73
(t, J = 50.0
Hz).
30
Compound 15: A
solution of 13 (64 mg, 0.10 mmol) in 0.1 M
80% HOAc was stirred at r.t. for 15 min, then was neutralized
with 1 M NaHCO3 and extracted with EtOAc. Purification
by radial chromatography (Merck silica gel 60 F254, eluent:
CH2Cl2-CH3OH, 25:1) gave 14 (19 mg, 63% yield). Then, a
solution of 10% NH4OH (1 mL) was added to 14 (10 mg, 0.03 mmol) in MeOH. The mixture
was kept at r.t. for 1 h. Purification by preparative chromatography (Merck
silica gel 60 F254, eluent: CH2Cl2-CH3OH,
10:1) gave 15 as an inseparable α/β mixture
(5 mg, 69% yield).
1H NMR
(400 MHz, CDCl3): δ (ppm) = 8.09 (d,
1 H, J = 7.2 Hz,
H-6a), 7.60 (d, 1 H, J = 8.0
Hz, H-6b), 5.78 (d, 1 H, H-5a), 5.74 (d, 1 H, H-5b), 4.81-4.60
(m, 4 H, H-1′a, H-1′b), 4.39-4.33, 4.21-4.18
(2 m, 2 H, H-5′a, H-5′b), 3.76-3.55 (m,
4 H, H-6′a, H-6′b), 2.65-2.63, 2.51-2.48
(2 m, 4 H, H-3′a, H-3′b), 2.01-1.98,
1.86-1.83 (2 m, 4 H, H-4′a, H-4′b).
19F
NMR (400 MHz, CDCl3): δ (ppm) = -225.40
(t, J = 50.0 Hz), -226.12
(t, J = 50.4
Hz).