NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
9
aromatic), 7.57 (t, J ¼ 8.0 Hz, 1 H, aromatic), 7.45 (dd, J ¼ 8.0, 8.0 Hz, 2 H,
aromatic), 7.32 (d, J ¼ 8.4 Hz, 2 H, aromatic), 4.58 (m, 2 H, –OCH O–),
2
4
.26 (d, J ¼ 11.6 Hz, 1 H, BzOCH C–), 4.13–4.21 (m, 3 H, –CHCH O–,
2
2
BzOCH C–), 3.69 (d, J ¼ 11.2 Hz, 1 H, MOMOCH C–), 3.48 (d, J ¼ 11.2 Hz,
2
2
1
1
H, MOMOCH C–), 3.31 (s, 3 H, CH O–), 2.43 (s, 3 H, CH Ph–), 1.36 (m,
2 3 3
H, –CCH(CH )CH –), 0.99 (dd, J ¼ 8.8, 5.8 Hz, 1 H, –CCH CH–), 0.55
2
2
2
(
dd, J ¼ 5.8, 5.6 Hz, 1 H, –CCH CH–); 13C NMR (CDCl , 100 MHz) d
2
3
1
6
4
66.3, 144.7, 133.3, 133.0, 130.0, 129.8, 129.5, 128.4, 127.8, 96.3, 70.6, 68.1,
6.9, 55.3, 25.2, 21.6, 20.0, 14.3; HRMS (ESI) calcd for C H O NaS:
2
2
26 7
þ
57.12914, found for 457.12915 [(M þ Na) ].
(
1R,2R)-{1-Benzoyloxymethyl-2-(adenin-9-yl)methyl-1-(methoxymethy-
loxy)-methyl}cyclopropane (14) and (1 R,2R)-{1-benzoyloxymethyl-2-
adenin-7-yl)methyl-1-(methoxymethyloxy)-methyl}cyclopropane (15). To
(
a solution of adenine (9.72 mg, 71.9 lmol) in DMF (0.25 mL) was added
NaH (60% dispersion in mineral oil, 2.88 mg, 71.9 lmol) at room tempera-
ture. After stirring the mixture at room temperature for 30 min, to the mix-
ture was added a solution of 2 (28.4 mg, 65.4 lmol) in DMF (0.10 mL) at
ꢁ
room temperature. After stirring the mixture at 50 C for 4 h, the resulting
mixture was partitioned between 50% AcOEt in hexane and saturated aque-
ous NaHCO . The organic layer was washed with brine, dried over anhyd-
3
rous Na SO , and evaporated in vacuo. The residue was purified by silica
2
4
gel column chromatography (5–9% MeOH in CHCl ) to give 14 (9.33 mg,
3
2
3.5 lmol, 36%) as a colorless waxy solid and 15 (3.12 mg, 7.83 lmol, 12%)
1
as a colorless waxy solid. 14: H NMR (400 MHz, CDCl ) d 8.36 (s, 1 H,
3
adenine-H2), 8.07 (s, 1 H, adenine-H8), 7.96 (d, J ¼ 8.0 Hz, 2 H, aromatic),
7
5
–
.56 (t, J ¼ 7.7 Hz, 1 H, aromatic), 7.44 (dd, J ¼ 8.0, 7.7 Hz, 2 H, aromatic),
.82 (s, 2 H, NH –), 4.64 (s, 2 H, –OCH O–), 4.38–4.44 (m, 2 H,
2
2
CHCH N–, BzOCH C–), 4.26 (dd, J ¼ 14.8, 8.0 Hz, 1 H, –CHCH N–),
2
2
2
4
.19 (d, J ¼ 11.6 Hz, 1 H, BzOCH C–), 4.02 (d, J ¼ 11.0 Hz, 1 H,
2
MOMOCH C–), 3.60 (d, J ¼ 11.0 Hz, 1 H, MOMOCH C–), 3.33 (s, 3 H,
2
2
CH O–), 1.61 (m, 1 H, –CCH(CH )CH –), 1.07 (dd, J ¼ 9.0, 5.9 Hz, 1 H,
3
2
2
–
CCH CH–), 0.79 (dd, J ¼ 5.9, 5.6 Hz, 1 H, –CCH CH–); UV (water) k
2
2
max
1
261 nm. 15: H NMR (400 MHz, CDCl ) d 8.51 (s, 1 H, adenine-H2), 8.14
3
(
1
s, 1 H, adenine-H8), 7.99 (d, J ¼ 8.4 Hz, 2 H, aromatic), 7.69 (t, J ¼ 8.0 Hz,
H, aromatic), 7.47 (dd, J ¼ 8.4, 8.0 Hz, 2 H, aromatic), 5.40 (s, 2 H,
NH –), 4.67 (s, 2 H, –OCH O–), 4.58 (dd, J ¼ 15.2, 6.5 Hz, 1 H,
2
2
–
6
CHCH N–), 4.43 (d, J ¼ 11.8 Hz, 1 H, BzOCH C–), 4.34 (dd, J ¼ 15.2,
2
2
.5 Hz, 1 H, –CHCH N–), 4.21 (d, J ¼ 11.8 Hz, 1 H, BzOCH C–), 4.10 (d,
2
2
J ¼ 11.0 Hz,
1 H,
MOMOCH C–),
3.54
(d,
J ¼ 11.0 Hz,
1 H,
2
MOMOCH C–), 3.36 (s, 3 H, CH O–), 1.57 (m, 1 H, –CCH(CH )CH –),
2
3
2
2
1
–
.16 (dd, J ¼ 9.0, 5.8 Hz, 1 H, –CCH CH–), 0.82 (dd, J ¼ 6.0, 5.6 Hz, 1 H,
2
CCH CH–); UV (water) k
265 nm.
max
2