Deoxygenative Functionalization of Hydroxy Groups via Xanthates with Tetraphenyldisilane

Full text of DOI:10.1021/jo991715r

2816
J . Org. Chem. 2000, 65, 2816-2819
Deoxygen a tive F u n ction a liza tion of
Hyd r oxy Gr ou p s via Xa n th a tes w ith
Tetr a p h en yld isila n e
Hideo Togo,*,†,‡ Sou Matsubayashi,†
Osamu Yamazaki,† and Masataka Yokoyama†,‡
Graduate School of Science and Technology, and
Department of Chemistry, Faculty of Science,
Chiba University, Yayoi-cho 1-33, Inage-ku,
Chiba, 263-8522, J apan
Received November 2, 1999
Deoxygenation reactions of hydroxy groups in carbo-
hydrates, nucleosides, and antibiotics are very important
due to their functional conversion. Today, the most
effective and practical deoxygenation method of hydroxy
groups is the Barton-McCombie reaction, which is the
reaction of xanthates with a tributyltin hydride/AIBN or
tributyltin hydride/Et3B system1 or, recently, phenylsi-
lane or diphenylsilane in the presence of peroxide or
Et3B,2 trialkylsilane in the presence of peroxide/thiol
(polarity reversal catalyst),3 5,10-dihydrosilanthrene/
AIBN,4 tris(trimethylsilyl)silane/AIBN,5 dibutylphos-
phine oxide/AIBN or Et3B,6 or phosphine-borane/AIBN.7
The Barton-McCombie reaction and the modified Bar-
ton-McCombie reaction with alternative reagents have
found widespread use in organic synthesis. However, it
is well-known that there are several problems in the use
of tributyltin hydride, such as toxicity and disposal,
workup, and complete removal of the tin species from the
products. Phenylsilane, diphenylsilane, and dibutylphos-
phine oxide are not so reactive, though these compounds
are much less toxic than the tin compound. Moreover,
these systems are limited to the deoxygenation reaction.
To our knowledge, only a few reports for the inter-
molecular addition reaction of sugar xanthate to electron
deficient olefins with tributyltin hydride in moderate
F igu r e 1.
yields have been made.8 Recently, we have reported the
utilization of tetraaryl disilanes, which are air-stable
crystals, for three types of radical reactions with alkyl
bromides, such as reduction, reductive addition to olefins,
and alkylation of heteroaromatic bases.9 Here, as part
of our program to develop the synthetic use of tetraaryl
disilanes for organic synthesis as an environmentally
benign system, we would like to report a new deoxygen-
ative formation of alkyl radicals from alcohols via xan-
thates, and their reduction to the corresponding hydro-
carbons, reductive addition to an activated olefin, and
alkylation of heteroaromatic bases, with tetraphenyl-
disilane as shown in Figure 1.
At first, reactivities of disilanes 1a -d in the reduction
of xanthate 2 derived from diacetone-D-glucose, in the
presence of AIBN in ethyl acetate were studied (entries
2-5). Disilanes 1a , 1b, and 1d showed excellent reactiv-
ity, while disilane 1c showed moderate reactivity as
shown in Table 1. Thus, disilanes 1a , 1b, and 1d are the
most effective reagent for the deoxygenative reduction
of xanthates 2. However, the preparation of disilane 1a
is much easier and more practical than that of disilanes
1b-d . Thus, disilane 1a was used for the deoxygenative
reduction of other xanthates 2, which were derived from
tertiary and secondary alcohols, and sugar compounds,
to give the corresponding reduction products in good
yields, though the same reaction of xanthate derived from
tridecanol, a primary alcohol, gave the reduction product
in moderate yield (entry 15). An imidazole thiocarbonyl
group can be also used instead of a methyl dithiocarbon-
ate group (entries 6 and 13). The present radical reaction
was carried out in ethyl acetate from the environmental
point of view. However, the same treatment of xanthates
in benzene gave the corresponding reduction product in
* To whom correspondence should be addressed. E-mail: togo@
scichem.s.chiba-u.ac.jp.
† Graduate School of Science and Technology.
‡ Department of Chemistry.
(1) (a) Barton, D. H. R.; McCombie, S. W. J . Chem. Soc., Perkin
Trans. 1 1975, 1574. (b) Barton, D. H. R.; Motherwell, W. B.; Stange,
A. Synthesis 1981, 743. (c) Rasmussen, J . R.; Slinger, C. J .; Kordish,
R. J .; Newman-Evans, D. D. J . Org. Chem. 1981, 46, 4843. (d) Barton,
D. H. R.; Hartwig, W.; Hay-Motherwell, R. S.; Motherwell, W. B.;
Stange, A. Tetrahedron Lett. 1982, 23, 2019. (e) Robins, M. J .; Wilson,
J . S.; Hansske, F. J . Am. Chem. Soc. 1983, 105, 4059. (f) Barton, D.
H. R.; Crich, D.; Lobberding, A.; Zard, S. Z. Chem. Commun. 1985,
646. (g) Barton, D. H. R.; Crich, D.; Lobberding, A.; Zard, S. Z.
Tetrahedron 1986, 42, 2329. (h) Nozaki, K.; Oshima, K.; Utimoto, K.
Tetrahedron Lett. 1988, 29, 6125. (i) Barton, D. H. R.; J aszberenyi, J .
C. Tetrahedron Lett. 1989, 30, 2619. (j) Barton, D. H. R.; J ang, D. O.;
J aszberenyi, J . C. Tetrahedron Lett. 1990, 31, 3991. (k) Barton, D. H.
R.; Parekh, S. I.; Tse, C.-L. Tetrahedron Lett. 1993, 34, 2733.
(2) (a) Barton, D. H. R.; J ang, D. O.; J aszberenyi, J . C. Tetrahedron
Lett. 1990, 31, 4681. (b) Barton, D. H. R.; J ang, D. O.; J aszberenyi, J .
C. Synlett 1991, 435.
(3) (a) Cole, S. J .; Kirwan, J . N.; Roberts, B. P.; Willis, C. R. J . Chem.
Soc., Perkin Trans. 1 1991, 103. (b) Allen, R. P.; Roberts, B. P.; Willis,
C. R. Chem. Commun. 1989, 1387.
(4) Gimisis, T.; Ballestri, M.; Ferreri, C.; Chatgilialoglu, C. Tetra-
hedron Lett. 1995, 36, 3897.
(8) (a) Giese, B.; Antonio, J .; Gomez, G.; Witzel, T. Angew. Chem.,
Int. Ed. Engl. 1984, 23, 69. (b) Dupuis, J .; Giese, B.; Hartung, J .;
Leising, M. J . Am. Chem. Soc. 1985, 107, 4332. (c) Araki, Y.; Endo, T.;
Tanji, M.; Nagasawa, J .; Ishido, Y. Tetrahedron Lett. 1987, 28, 5853.
(d) Blattner, R.; Ferrier, R. J .; Renner, R. J . Chem. Soc., Chem.
Commun. 1987, 1007. (e) Araki, Y. Endo, T.; Tanji, M.; Nagasawa, J .;
Ishido, Y. Tetrahedron Lett. 1988, 29, 351.
(9) (a) Yamazaki, O.; Togo, H.; Matsubayashi, S.; Yokoyama, M.
Tetrahedron Lett. 1998, 39, 1921. (b) Yamazaki, O.; Togo, H.; Mat-
subayashi, S.; Yokoyama, M. Tetrahedron 1999, 55, 3735.
(5) Chatgilialoglu, C. Acc. Chem. Res. 1992, 25, 188.
(6) (a) Barton, D. H. R.; J ang, D. O.; J aszberenyi, J . C. Tetrahedron
Lett. 1992, 33, 5709. (b) J ang, D. O.; Cho, D. H.; Barton, D. H. R. Synlett
1998, 39.
(7) Barton, D. H. R.; J acob, M. Tetrahedron Lett. 1998, 39, 1331.
10.1021/jo991715r CCC: $19.00 © 2000 American Chemical Society
Published on Web 04/05/2000

Notes
Ta ble 1. Red u ction of Xa n th a tes w ith Disila n esa
J . Org. Chem., Vol. 65, No. 9, 2000 2817
Ta ble 2. Red u ctive Ad d ition to P h en yl Vin yl Su lfon ea
a
Key: (i) xanthate/olefin/disilane/AIBN ) 0.2/0.6/0.5/0.1 (mmol).
presence of AIBN was carried out to give the correspond-
ing alkylated compounds 5 in moderate yields, though
again the same reactions with xanthates derived from
primary alcohols gave poor results. Here the formation
of reduction products 3 as a byproduct was observed (24-
46%).
In conclusion, the present three types of deoxygenative
reactions, such as reduction, reductive addition to electron-
deficient olefins, and alkylation of heteroaromatic bases
with xanthates in the presence of tetraphenyldisilane and
AIBN have been achieved in ethyl acetate, as an envi-
ronmentally benign system.
a
Key: (i) xanthate/disilane/AIBN ) 0.20/0.22/0.06 (mmol); (ii)
reaction was carried out in benzene, instead of ethyl acetate; (iii)
reaction was carried out at room temperature with triethylborane
(1.2 mmol), instead of AIBN.
Exp er im en ta l Section
good yields (entry 7). Moreover, the same reduction of
xanthate in the presence of disilane 1a at room temper-
ature using triethylborane, instead of AIBN, proceeded
effectively to give the corresponding reduction product
in good yield (entry 9). As a typical addition reaction, the
addition reaction of xanthates 2 to phenylvinyl sulfone
under the same system was carried out. The results are
shown in Table 2. Disilanes 1a and 1b showed moderate
reactivity to give the corresponding reductive addition
products in moderate yields, while disilanes 1c and 1d
were not so effective (entries 3-6). The reductive addition
of other xanthates 2 to phenylvinyl sulfone using disilane
1a in the presence of AIBN was carried out to give the
corresponding reductive addition products in moderate
yields, together with the reduction products 3 (20-42%).
Diethylvinyl phosphonate also showed the same reactiv-
ity.
Gen er a l Meth od s. 1H NMR and 29Si NMR spectra were
recorded on 400 and 500 MHz spectrometers, and 13C NMR
spectra were recorded on 100 and 125 MHz spectrometers.
Chemical shifts are reported as ppm downfield from tetrameth-
ylsilane (TMS) in δ units. J values are given in Hz. The matrix
of mass spectra (FAB) used 3-nitrobenzyl alcohol, and the source
of the K in the FAB MS was KI. Microanalysis was performed
at the Chemical Analysis Center of Chiba University. GC spectra
were recorded with packed column (OV-17 and SE-30). Melting
points were determined on an electrochemical apparatus in open
capillary tubes and are uncorrected. Kieselgel 60 F254 was used
for TLC, Wakogel C-200 was used for column chromatography,
and Wakogel B-5F was used for pTLC.
Ma ter ia ls. Most of the alkyl halides and simple organic
chemicals were commercially available. The following com-
pounds were prepared according to the procedures described in
the literature.
Tetraphenyldisilane: mp 76.5-80.5 °C (lit.10 mp 79-80 °C);
IR 2120 cm-1 (SiH); (CDCl3, TMS) 1H NMR δ ) 5.19 (s, SiH),
29Si NMR δ ) -34.96. Tetra(p-methoxyphenyl)disilane: mp
Finally, in the alkylation (substitution) of heteroaro-
matic bases, the alkylation of typical heteroaromatic
bases with tetraphenyldisilane and xanthates in the
122.1-124.3 °C; IR 2100 cm-1 (SiH); (CDCl3, TMS) H NMR δ
1
) 5.12 (s, SiH), 29Si NMR δ ) -36.45. Tetra(p-fluorophenyl)-

2818 J . Org. Chem., Vol. 65, No. 9, 2000
Notes
Ta ble 3. Alk yla tion on to Heter oa r om a tic Ba sesa
ature under an argon atmosphere. After the reaction, solvent
was removed and the residue was purified by pTLC or column
chromatography on silica gel.
Gen er a l P r oced u r e for Alk yla tion of Heter oa r om a tic
Ba ses w ith Or ga n od isila n e a n d AIBN u n d er Th er m a l
Con d ition s. AIBN (0.1 mmol) was added five times over 8 h (2
h intervals) to a solution of a heteroaromatic base (1.0 mmol),
xanthate (0.2 mmol), and organodisilane (0.5 mmol) in ethyl
acetate at refluxing temperature. Then, the solution was stirred
for 16 h at the same temperature. The resulting solution was
quenched with saturated aqueous sodium hydrogen carbonate.
The organic layer was extracted with ethyl acetate and dried
over Na2SO4. After removal of the solvent, the residue was
purified by pTLC or column chromatography on silica gel.
Ch olesta n e: mp 77.5-79.0 °C; IR (KBr) 2930, 2850, 1470,
1440, 1380 cm-1; 1H NMR (CDCl3) δ ) 0.61-1.98 (33H, m), 0.64
(3H, s), 0.77 (3H, s), 0.85 (3H, d, J ) 1.7 Hz), 0.87 (3H, d, J )
1.7 Hz), 0.90 (3H, d, J ) 6.5 Hz); 13C NMR (CDCl3) δ ) 12.09
(p), 12.24 (p), 18.68 (p), 20.82 (s), 22.21 (s), 22.58 (p), 22.83 (p),
23.85 (s), 24.20 (s), 26.87 (s), 28.02 (t), 28.27 (s), 29.08 (s), 29.12
(s), 32.20 (s), 35.54 (t), 35.82 (t), 36.19 (s), 36.25 (q), 38.71 (s),
39.53 (s), 40.14 (s), 42.60 (q), 47.05 (t), 54.78 (t), 56.31 (t), 56.65
(t). Anal. Calcd for C27H48: C, 87.02; H, 12.98. Found: C, 86.91;
H, 13.13.
2,3,4,6-Tetr a -O-a cetyl-1,5-a n h yd r o-D-glu citol: mp 66.0-
67.5 °C (lit.11 mp 71-73 °C); 1H NMR (CDCl3) δ ) 2.03 (3H, s),
2.04 (6H,s), 2.10 (3H, s), 3.31 (1H, t, J ) 11.0 Hz), 3.58-3.62
(1H, m), 4.04-4.23 (3H, m), 4.98-5.09 (2H, m), 5.21 (1H, t, J )
9.5 Hz); MS (FAB) found (M + H) m/z 333.
1-Deoxy-2,3,5,6-d i-O-isop r op ylid en e-r-D-r ibo-h exofu r a -
n ose: oil; IR (neat) 1460, 1370, 1210, 1070 cm-1 1H NMR
;
(CDCl3) δ ) 1.34 (3H, s), 1.38 (3H, s), 1.45 (3H, s), 1.49 (3H, s),
3.48 (1H, dd, J ) 7.1, 3.7 Hz), 3.50 (1H, dd, J ) 10.7, 3.5 Hz),
4.01-4.14 (3H, m), 4.42 (1H, ddd, J ) 6.8, 5.9, 5.0 Hz), 4.73 (1H,
dd, J ) 6,1, 3.7 Hz), 4.79 (1H, dd, J ) 6.2, 3.6 Hz); 13C NMR
(CDCl3) δ ) 24.50 (p), 25.23 (p), 25.88 (p), 26.91 (p), 66.81 (s),
73.11 (s), 73.25 (t), 80.33 (t), 81.00 (t), 82.77 (t), 109.01 (q),
112.33(q); HRMS(FAB) found m/z 283.0921, calcd for C12H20O5K
(M + K) 283.0948.
a
3-Deoxy-1,2,5,6-d i-O-isop r op ylid en e-r-D-r ibo-h exofu r a -
Key: (i) xanthate/salt/1a /AIBN ) 0.2/1.0/0.5/0.5 (mmol); f,
1
C-C bond-forming position.
n ose: oil; IR (neat) 1370, 1210, 1060 cm-1; H NMR (CDCl3) δ
) 1.25 (3H, s), 1.29 (3H, s), 1.36 (3H, s), 1.45 (3H, s), 1.70 (1H,
ddd, J ) 13.5, 10.1, 4.9 Hz), 2.12 (1H, dd, J ) 13.4, 4.0 Hz),
3.72-3.79 (1H, m), 4.01-4.13 (3H, m), 4.69 (1H, t, J ) 4.2 Hz),
5.72 (1H, d, J ) 3.7 Hz); 13C NMR (CDCl3) δ ) 25.18 (p), 26.15
(p), 26.48 (p), 26.78 (p), 35.26 (s), 67.21 (s), 76.84 (t), 78.66 (t),
80.45 (t), 105.63 (t), 109.67 (q), 111.33(q); HRMS(FAB) found
m/z 283.0939, calcd for C12H20O5K (M + K) 283.0948.
disilane: mp 105.1-106.0 (lit.10 mp 116 °C); IR 2115 cm-1 (SiH)
1H NMR δ ) 5.15 (s, SiH), 29Si NMR δ ) -35.55. Diphenyldi-
methyldisilane: oil; IR 2110 cm-1 (SiH); (CDCl3, TMS) 1H NMR
δ ) 4.36-4.44 (m, SiH), 29Si NMR δ ) -36.37 and -36.80.
Gen er a l P r oced u r e for th e P r ep a r a tion of Xa n th a tes
fr om th e Cor r esp on d in g Alcoh ols. A mixture of alcohol (10
mmol), sodium hydride (60%; 29.2 mmol), and imidazole (0.29
mmol) in tetrahydrofuran (50 mL) was stirred for 3 h under an
argon atmosphere at room temperature. Carbon disulfide (49.9
mmol) was added and the mixture stirred for 0.5 h. Then, methyl
iodide (48.2 mmol) was added and the mixture stirred for 0.5 h.
The reaction mixture was quenched with acetic acid (52. 4
mmol), and the resulting solution was worked up in the usual
way. The organic layer was extracted with ethyl acetate and
dried over Na2SO4. After removal of solvent, the residue was
purified by pTLC or column chromatography on silica gel to give
the xanthate in quantitative yield.
Gen er a l P r oced u r e for Ra d ica l Red u ction w ith Or ga -
n od isila n es. A solution of xanthate (0.2 mmol), tetraphenyld-
isilane (0.22 mmol), and AIBN (0.06 mmol) in ethyl acetate (1.5
mL) was refluxed for 16 h under an argon atmosphere. After
the reaction, the solvent was removed, and the residue was
chromatographed on silica gel.
Gen er a l P r oced u r e for Ra d ica l Ad d ition to P h en yl
Vin yl Su lfon e w ith Or ga n od isila n es u n d er Th er m a l Con -
d ition s. A mixture of xanthate (0.2 mmol), phenyl vinyl sulfone
(0.6 mmol), organodisilane (0.5 mmol), and AIBN (0.1 mmol) in
ethyl acetate (1.5 mL) was stirred for 16 h at refluxing temper-
2-(1-Ad a m a n tyl)eth yl p h en yl su lfon e: mp 103.5-105.5 °C
1
(lit.12 mp 101.4-103.5 °C); H NMR (CDCl3) δ ) 1.40 (6H, d, J
) 2.4 Hz), 1.45-1.50 (2H, m), 1.57 (3H, d, J ) 11.5 Hz), 1.68
(3H, d, J ) 12.2 Hz), 1.93 (3H, bs), 3.04-3.08 (2H, m), 7.55-
7.59 (2H, m), 7.64-7.68 (1H, m), 7.89-7.92 (2H, m); MS (FAB)
found (M + H) m/z 305.
Dieth yl 2-(1-a d a m a n tyl)eth ylp h osp h on a te: oil;12 IR (neat)
1450, 1240, 1035, 960 cm-1 1H NMR (CDCl3) δ ) 1.31-1.39
;
(2H, m), 1.33 (6H, t, J ) 7.1 Hz), 1.45 (6H, d, J ) 2.4 Hz), 1.59-
1.72 (8H, m), 1.96 (3H, bs), 4.02-4.16 (4H, m); MS (EI) found
m/z 300.
2-Cycloh exyleth yl p h en yl su lfon e: oil;12 IR (neat) 1445,
1310, 1150, 1085 740, 690 cm-1 1H NMR (CDCl3) δ ) 0.81-
;
0.90 (2H, m) 1.08-1.34 (3H, m), 1.55-1.69 (8H, m), 3.07-3.12
(2H, m), 7.55-7.59 (2H, m), 7.64-7.68 (1H, m), 7.90-7.92 (2H,
m); 13C NMR (CDCl3) δ ) 25.98 (s), 26.25 (s), 29.61 (s), 32.76
(s), 36.62 (t), 54.37 (s), 128.03 (t), 129.25 (t), 133.59 (t), 139.28
(q); MS (FAB) found (M + H) m/z 253.
2-(3-Ch olesta n yl)eth yl p h en yl su lfon e: mp 116.0-119.5
°C; IR (KBr) 1445, 1375, 1305, 1240, 1150, 740, 690 cm-1 1H
;
NMR (CDCl3) δ ) 0.63 (3H, s), 0.70 (3H, s), 0.85 (3H, d, J ) 1.8
Hz), 0.87 (3H, d, J ) 1.8 Hz), 0.89 (3H, d, J ) 6.6 Hz), 0.75-
2.00 (34H, m), 3.07 (2H, m), 7.55-7.59 (2H, m), 7,64-7.68 (1H,
(10) (a) Steudel, W.; Gilman, H. J . Am. Chem. Soc. 1960, 82, 6129.
(b) Winkler, H. J . S.; Gilman, H. J . Org. Chem. 1961, 26, 1265. (c)
Schott, V. G.; Langecker, W. Anorg. Allg. Chem. 1968, 358, 210. (d)
Linke, Karl-H.; Go¨hausen, H. J . Chem. Ber. 1973, 106, 3438. (e) Gerval,
P.; Frainnet, E.; Lain, G.; Moulines, F. Bull. Soc. Chim. Fr. 1974, 7,
1548. (f) Boudjouk, P. Han, B. H. Tetrahedron Lett. 1981, 22, 3813.
(11) Auge´, J .; David, S. Carbohydr. Res. 1977, 59, 255.
(12) (a) Togo, H.; Aoki, M.; Yokoyama, M. Tetrahedron 1993, 49,
8241. (b) Togo, H.; Aoki, M.; Yokoyama, M. J . Chem. Soc., Perkin Trans.
1 1993, 2417. (c) Togo, H.; Hayashi, K.; Yokoyam, M. Bull. Chem. Soc.
J pn. 1994, 67, 2522.

Notes
J . Org. Chem., Vol. 65, No. 9, 2000 2819
m), 7.89-7.92 (2H, m); 13C NMR (CDCl3) δ ) 12.01 (p), 12.25
(p), 18.67 (p), 20.99 (s), 22.56 (p), 22.82 (p), 23.83 (s), 24.18 (s),
28.01 (t), 28.23 (s), 28.43 (s), 28.88 (s), 29.59 (s), 32.05 (s), 35.11
(q), 35.49 (s), 35.79 (t), 35.96 (t), 36.17 (s), 37.02 (t), 38.24 (s),
39.51 (s), 40.04 (s), 42.57 (q), 46.36 (t), 54.46 (t), 54.50 (s), 56.27
(t), 56.53 (t), 128.05 (t), 129.25 (t), 133.58 (t), 139.24 (q). Anal.
Calcd for C35H56O2S: C,77.72; H, 10.44. Found: C, 77.89; H,
10.56.
Hz), 8.05 (1H, dd, J ) 8.4, 1.0 Hz); 13C NMR (CDCl3) δ ) 18.80
(p), 26.10 (s), 26.53 (s), 32.80 (s), 47.55 (t), 120.21 (t), 123.52 (t),
125.33 (t), 127.01 (q), 128.90 (t), 129.45 (t), 144.21 (q), 147.58
(q), 166.49(q); MS (EI) found m/z 225.
2-(3-Ch olesta n yl)-4-m eth ylqu in olin e: mp 186.0-187.5 °C
(lit.12 mp 182.0-184.0 °C); 1H NMR (CDCl3) δ ) 0.68 (3H, s),
0.86 (3H, d, J ) 1.7 Hz), 0.88 (3H, d, J ) 1.7 Hz), 0.92 (3H, d,
J ) 6.6 Hz), 0.94 (3H, s), 0.71-2.05 (31H, m), 2.69 (3H, s), 2.92
(1H, m), 7.19 (1H, s), 7.49 (1H, ddd, J ) 8.3, 6.9, 1.0 Hz), 7.66
(1H, ddd, J ) 8.4, 6.9, 1.2 Hz), 7.94 (1H, dd, J ) 8.3, 1.2 Hz),
8.04 (1H, dd, J ) 8.4, 1.0 Hz); MS (EI) found m/z 513.
2-(1-Ad a m a n tyl)ben zoth ia zole: mp 103.5-104.5 °C (lit.12
mp 102.3-104.2 °C); 1H NMR (CDCl3) δ ) 1.82 (6H, bs), 2.16
(9H, bs), 7.33 (1H, ddd, J ) 8.1, 7.2, 1.1 Hz), 7.44 (1H, ddd, J )
8.3, 7.2, 1.2 Hz), 7.86 (1H, dd, J ) 8.1, 1.2 Hz), 8.0 (1H, dd, J )
8.3, 1.1 Hz); MS (EI) found m/z 269.
n -Decyl p h en yl su lfon e: oil;9 IR (neat) 1445, 1305, 1150,
740, 690 cm-1 1H NMR (CDCl3) δ ) 0.87 (3H, t, J ) 6.9 Hz),
;
1.22-1.34 (14H, m), 1.67-1.74 (2H, m), 3.06-3.10 (2H, m),
7.56-7.58 (2H, m), 7.66 (1H, t, J ) 7.5 Hz), 7.90-7.92 (2H, m);
13C NMR (CDCl3) δ ) 14.10 (p), 22.64 (s), 28.27 (s), 28.99 (s),
29.22 (s), 29.42 (s), 31.83 (s), 56.35 (s), 128.07 (t), 129.26 (t),
133.60 (t), 139.29(q); MS (FAB) found (M + H) m/z 283.
2-Cyclod od ecyleth yl p h en yl su lfon e: mp 95.5-97.1 °C; IR
(KBr) 1480, 1450, 1300, 1140, 1080, 750, 690, cm-1 1H NMR
;
2-(1-Ad a m a n tyl)p yr id in e: mp 36.0-38.5 °C (lit.12 mp 33.0-
37.0 °C); 1H NMR (CDCl3) δ ) 1.79 (6H, d, J ) 2.7 Hz), 2.00
(6H, d, J ) 3.1 Hz), 2.11 (3H, bs), 7.08 (1H, ddd, J ) 7.7, 4.8,
1.0 Hz), 7.27 (1H, dt, J ) 7.7, 1.0 Hz), 7.62 (1H, td, J ) 7.7, 1.9
Hz), 8.58 (1H, ddd, J ) 4.8, 1.9, 1.0 Hz); MS (EI) found m/z 213.
4-(1-Ad a m a n tyl)p yr id in e: mp 75.5-77.0 °C (lit.12 mp 75.0-
(CDCl3) δ ) 1.10-1.34 (22H, m), 1.40-1.51 (1H, m), 1.59-1.67
(2H, m), 3.06-3.12 (2H, m), 7.54-7.60 (2H, m), 7.62-7.68 (1H,
m) 7.89-7.93 (2H,m); 13C NMR (CDCl3) δ ) 21.44 (s), 23.16 (s),
23.22 (s), 24.09 (s), 24.63 (s), 27.33 (s), 28.61 (s), 33.30 (t), 54.73
(s), 128.03 (t), 129.23 (t), 133.55 (t), 139.31 (q); MS (FAB) found
(M + H) m/z 337. Anal. Calcd for C20H32O2S: C, 71.38; H, 9.58.
Found: C, 71.18; H, 9.62.
1
78.0 °C); H NMR (CDCl3) δ ) 1.75 (3H, d, J ) 12.4 Hz), 1.81
(3H, d, J ) 12.4 Hz), 1.89 (6H, d, J ) 2.7 Hz), 2.12 (3H, bs),
7.25 (2H, dd, J ) 4.6, 1.7 Hz), 8.51 (2H, dd, J ) 4.6, 1.7 Hz); MS
(EI) found m/z 213.
2-[1-(2,3,5,6-Di-O-isopr opyliden e-r-D-r ibo-h exofu r an osyl)]-
eth yl p h en yl su lfon e: mp 105.1-106.0 °C; IR (KBr) 1580, 1450,
1
1310, 1280, 1210, 1150, 1080, 750, 690 cm-1; H NMR (CDCl3)
2-Cyclod od ecyl-4-m eth ylqu in olin e: mp 99.5-100.3 °C; IR
(KBr) 1600, 1470, 1440, 760, cm-1; 1H NMR (CDCl3) δ ) 1.20-
1.80 (20H, m), 1.85-1.97 (2H, m), 2.68 (3H, s), 3.05-3.14 (1H,
m) 7.13 (1H, s), 7.48 (1H, ddd, J ) 8.3, 7.0, 1.2 Hz), 7.65 (1H,
ddd, J ) 8.5, 7.0, 1.4 Hz) 7.94 (1H, dd, J ) 8.5, 1.0 Hz), 8.06
(1H, dd, J ) 8.5, 0.5 Hz); 13C NMR (CDCl3) δ ) 18.77 (p), 22.91
(s), 23.38 (s), 23.71 (s), 23.88 (s), 23.95 (s), 30.15 (s), 43.09 (t),
121.40 (t), 123.50 (t), 125.25 (t), 126.95 (q), 128.76 (t), 129.60
(t), 143.78 (q), 147.65 (q), 166.70(q); HRMS (FAB) found m/z
310.2524, calcd for C22H32N (M + H) 310.2535.
δ ) 1.31 (3H, s), 1.36 (3H, s), 1.42 (3H, s), 1.46 (3H, s), 1.81-
1.87 (2H, m), 3.07-3.14 (1H, m), 3.18-3.25 (1H, m), 3.65 (1H,
dd, J ) 7.4, 3.7 Hz), 3.93 (1H, dd, J ) 8.8, 4.6 Hz), 4.02 (1H, t,
J ) 7.8 Hz), 4.06 (1H, dd, J ) 8.8, 6.4 Hz), 4.33-4.38 (1H, m),
4.47 (1H, dd, J ) 6.1, 0.9 Hz), 4.74 (1H, dd, J ) 6.1, 3.7 Hz),
7.57-7.62 (2H, m), 7.65-7.70 (1H, m), 7.9-7.93 (2H, m); 13C
NMR (CDCl3) δ ) 23.74 (s), 24.59 (p), 25.10 (p), 26.03 (p), 26.83
(p), 52.90 (s), 66.78 (s), 73.16 (t), 80.18 (t), 80.50 (t), 82.36 (t),
84.98 (t), 109.19 (q), 112.94 (q), 127.93 (t), 129.41 (t), 133.85 (t),
138.87 (q); MS (FAB) found (M + H) m/z 413. Anal. Calcd for
C20H28O7S: C, 58.23; H, 6.84. Found: C, 57.94; H, 6.70.
2-(1-Ad a m a n tyl)-4-m eth ylqu in olin e: mp 115.5-121.5 °C
(lit.9 mp 120.3-122.0 °C); 1H NMR (CDCl3) δ ) 1.82 (6H, t, J )
3.0 Hz), 2.11 (6H, d, J ) 2.9 Hz), 2.15 (3H, bs), 2.68 (3H, d, J )
1.0 Hz), 7.32 (1H, d, J ) 1.0 Hz), 7.48 (1H, m), 7.64 (1H, m),
7.93 (1H, d, J ) 8.3 Hz), 8.06 (1H, d, J ) 8.2 Hz); MS (EI) found
m/z 277.
Ack n ow led gm en t. We are grateful for financial
support from a Grant-in-Aid for Scientific Research
(10640511) from the Ministry of Education, Science,
Sports and Culture of J apan.
1
Su p p or tin g In for m a tion Ava ila ble: Copies of H NMR
2-Cycloh exyl-4-m eth ylqu in olin e: oil;12 IR (neat) 1600,
1450, 760 cm-1; 1H NMR (CDCl3) δ ) 1.25-2.04 (10H, m), 2.83-
2.90 (1H, m), 7.17 (1H, s), 7.49 (1H, ddd, J ) 8.3, 6.9, 1.0 Hz),
7.66 (1H, ddd, J ) 8.4, 6.9, 1.2 Hz), 7.95 (1H, dd, J ) 8.3, 1.2
spectra for all products described in the paper. This material
is available free of charge via the Internet at http://pubs.acs.org.
J O991715R