M. Tiecco et al.
FULL PAPER
128.3 (2C), 128.2 (2C), 128.1 (4C), 127.3 (2C), 127.2, 127.1 (2C),
127.0, 126.7 (2C), 52.1, 51.9, 51.3, 50.4, 44.1, 44.0 (2C), 43.4, 43.2, H, CH), 7.50–7.41 (m, 2 H, CH), 3.97 (dd, JH,H = 4.4, JH,H
43.0, 21.4, 21.1, 13.9 ppm (2C). Elemental analysis for
C27H28O3SSe (511.5): calcd. C 63.40, H 5.52; found: C 63.54, H
5.68.
CDCl3, 25 °C, TMS): δ = 8.1–8.0 (m, 2 H, CH), 7.63–7.50 (m, 1
3
4
=
3
2.3 Hz, 1 H, CH), 3.94 (d, JH,H = 6.8 Hz, 1 H, CH), 3.78 (s, 3 H,
OCH3), 3.30 (dd, 2JH,H = 16.6, 3JH,H = 4.3 Hz, 1 H, CH2), 3.0 (dd,
2JH,H = 16.6, J H,H = 8.7 Hz, 1 H, CH2), 2.80–2.67 (m, 1 H, CH),
3
3
2.24 (t, JH,H = 4.4 Hz, 1 H, CH), 1.98–1.52 (m, 3 H, CH2), 1.50–
1.40 (m, 1 H, CH2), 1.19 (d, JH,H = 7.7 Hz, 3 H, CH3), 1.03 (s, 3
Methyl
(2S,3S)-2-(Camphorseleno)-5-oxo-3,5-diphenylpentanoate
3
(3c): Yield 69% (0.35 mmol, 178 mg), oil. [α]2D0 = –52.0 (c = 3.2 in
H, CH3), 0.93 (s, 3 H, CH3), 0.92 ppm (s, 3 H, CH3). 13C NMR
(100 MHz, CDCl3, 25 °C, TMS): δ = 216.9, 198.6, 173.3, 136.8,
132.9, 128.4 (2C), 128.0 (2C), 57.9, 53.0, 48.2, 47.5, 46.6, 45.7, 43.1,
31.0, 30.5, 23.3, 19.4, 19.3, 18.1, 9.4 ppm. MS (70 eV, EI): m/z (%):
450 (16) [M+], 418 (7), 400 (4), 331 (23), 299 (14), 267 (10), 231
(12), 219 (95), 187 (25), 159 (19), 120 (47), 105 (100), 77 (30), 55
(12). Elemental analysis for C23H30O4Se (449.4): calcd. C 61.46, H
6.73; found: C 61.35, H 6.82. anti isomer (distinct signals): 1H
1
CHCl3). H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 8.0–7.90
(m, 2 H, CH), 7.62–7.58 (m, 1 H, CH), 7.52–7.45 (m, 2 H, CH),
3
7.39–7.22 (m, 5 H, CH), 4.27 (d, JH,H = 8.8 Hz, 1 H, CH), 4.05
3
3
(ddd, JH,H = 9.6, 8.8 and 4.1 Hz, 1 H, CH), 3.83 (dd, JH,H = 4.3,
4JH,H = 2.2 Hz, 1 H, CH), 3.82 (s, 3 H, OCH3), 3.71 (dd, JH,H
=
=
2
3
2
3
16.8, JH,H = 9.6 Hz, 1 H, CH2), 3.51 (dd, JH,H = 16.8, JH,H
3
4.1 Hz, 1 H, CH2), 2.20 (t, JH,H = 4.3, 1 H, CH), 1.90–1.60 (m, 3
H, CH2), 1.42–1.30 (m, 1 H, CH2), 1.05 (s, 3 H, CH3), 0.95 (s, 3
H, CH3), 0.92 ppm (s, 3 H, CH3). 13C NMR (100 MHz, CDCl3,
25 °C, TMS): δ = 216.9, 197.5, 173.0, 140.7, 136.8, 133.1, 128.5
(2C), 128.4 (2C), 128.3 (2C), 128.1 (2C), 127.2, 58.1, 52.5, 48.2,
47.7, 46.8, 44.6, 43.1, 42.8, 30.4, 23.5, 19.6, 19.5, 9.6 ppm. MS
(70 eV, EI): m/z (%): 512 (4) [M+], 392 (8), 360 (3), 311 (8), 281
(33), 249 (21), 221 (4), 209 (5), 163 (7), 121 (7), 120 (12), 105 (100),
77 (18), 55 (5). Elemental analysis for C28H32O4Se (511.5): calcd.
C 65.75, H 6.31; found: C 65.50, H 6.15.
3
4
NMR: δ = 4.0 (dd, JH,H = 4.5, JH,H = 2.3 Hz, 1 H, CH), 3.77 (s,
2
3
3 H, OCH3), 3.68 (dd, JH,H = 17.0, JH,H = 4.1 Hz, 1 H, CH2),
2.91 (dd, JH,H = 17.0, JH,H = 8.6 Hz, 1 H, CH2), 2.26 (t, JH,H
4.5 Hz, 1 H, CH), 1.13 (d, JH,H = 6.5 Hz, 3 H, CH3), 0.96 (s, 3 H,
2
3
3
=
3
CH3), 0.94 (s, 3 H, CH3).
Methyl (2R*,3S*)-5-Oxo-3,5-diphenyl-2-(phenylseleno)pentanoate
(4a): Yield 67% (0.34 mmol, 147 mg, Table 1, entry 4), m.p. 88 °C.
1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.90–7.82 (m, 2 H,
CH), 7.68–7.61 (m, 2 H, CH), 7.56–7.50 (m, 1 H, CH), 7.45–7.10
(m, 10 H, CH), 4.04 (d, 3JH,H = 11.2 Hz, 1 H, CH), 4.03 (dd, 2JH,H
Methyl (2S,3S)-2-(Camphorseleno)-5-oxo-3-phenylhexanoate (3d):
Yield 61% (0.30 mmol, 137 mg), oil. [α]3D0 = –56.0 (c = 4.81 in
3
3
1
= 16.7, JH,H = 3.6 Hz, 1 H, CH2), 3.95 (ddd, JH,H = 11.2, 9.2
and 3.6 Hz, 1 H, CH), 3.47 (dd, 2JH,H = 16.7, 3JH,H = 9.2 Hz, 1 H,
CH2), 3.43 ppm (s, 3 H, OCH3). 13C NMR (100 MHz, CDCl3,
25 °C, TMS): δ = 197.4, 171.5, 140.7, 136.6, 134.8 (2C), 132.6,
128.9 (2C), 128.2 (2C), 128.1 (2C), 128.0 (2C), 127.6 (4C), 126.7,
51.5, 50.4, 43.1, 42.1 ppm. MS (70 eV, EI): m/z (%): 438 (1) [M+],
318 (18), 281 (45), 249 (12), 105 (100), 77 (26). Elemental analysis
for C24H22O3Se (437.4): calcd. C 65.90, H 5.07; found: C 66.0, H
5.18.
CHCl3). H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.40–7.15
3
3
(m, 5 H, CH), 4.11 (d, JH,H = 8.6 Hz, 1 H, CH), 3.78 (ddd, JH,H
= 9.2, 8.6 and 4.8 Hz, 1 H, CH), 3.74 (s, 3 H, OCH3), 3.72 (dd,
4
2
3JH,H = 4.3, JH,H = 2.2 Hz, 1 H, CH), 3.05 (dd, JH,H = 16.6,
3JH,H = 9.2 Hz, 1 H, CH2), 2.94 (dd, 2JH,H = 16.6, JH,H = 4.8 Hz,
3
1 H, CH2), 2.13 (t, 3JH,H = 4.3 Hz, 1 H, CH), 2.03 (s, 3 H, CH3CO),
1.82–1.72 (m, 1 H, CH2), 1.68–1.52 (m, 2 H, CH2), 1.38–1.28 (m,
1 H, CH2), 0.99 (s, 3 H, CH3), 0.89 (s, 3 H, CH3), 0.86 ppm (s, 3
H, CH3). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 216.8,
206.0, 172.7, 140.4, 128.7 (2C), 128.3 (2C), 127.1, 57.9, 52.2, 48.1,
47.5, 47.4, 46.6, 44.4, 42.6, 30.3, 30.2, 23.3, 19.5, 19.3, 9.5 ppm.
MS (70 eV, EI): m/z (%): 450 (19) [M+], 418 (7), 392 (5), 360 (4),
311 (9), 279 (8), 231 (20), 219 (60), 187 (100), 177 (41), 163 (60),
145 (17), 121 (37), 107 (10), 83 (13), 55 (15). Elemental analysis for
C23H30O4Se (449.4): calcd. C 61.46, H 6.73; found: C 61.40, H
6.59.
The δ-oxo ester 4a was converted into the following δ-lactone by
NaBH4 reduction followed by cyclisation by treatment with TFA
in toluene at reflux.[20]
(3R*,4S*,6R*)-4,6-diphenyl-3-(phenylseleno)tetrahydro-2H-pyran-2-
one: Yield 51% (0.05 mmol, 21 mg), oil. 1H NMR (400 MHz,
CDCl3, 25 °C, TMS): δ = 7.48–7.20 (m, 15 H, CH), 5.52 (dd, 3JH,H
= 11.8 and 4.2 Hz, 1 H, CH), 4.19 (dd, 3JH,H = 4.2, 4JH,H = 1.5 Hz,
Methyl (2S,3S)-2-(Camphorseleno)-5-oxo-3-(thien-2-yl)hexanoate
(3e): Yield 60% (0.30 mmol, 137 mg), oil. [α]2D7 = –71.9 (c = 3.9 in
3
1 H, CH), 3.84 (dt, JH,H = 11.8 and 4.2 Hz, 1 H, CH), 2.54 (dt,
3
2
2JH,H = 14.0, JH,H = 11.8 Hz, 1 H, CH2), 2.45 ppm (dtd, JH,H
=
1
CHCl3). H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.17 (dd,
3
4
3JH,H = 5.1, 4JH,H = 1.2 Hz, 1 H, CH), 6.96 (dd, 3JH,H = 3.6, 4JH,H
14.0, JH,H = 4.2, JH,H = 1.5 Hz, 1 H, CH2). Elemental analysis
3
for C23H20O2Se (407.4): calcd. C 67.81, H 4.95; found: C 67.75, H
5.0.
= 1.2 Hz, 1 H, CH), 6.92 (dd, JH,H = 5.1 and 3.6 Hz, 1 H, CH),
3
4
4.22–4.16 (m, 2 H, CH), 3.83 (dd, JH,H = 4.3, JH,H = 2.2 Hz, 1
H, CH), 3.76 (s, 3 H, OCH3), 3.12–3.02 (m, 2 H, CH2), 2.20 (t,
3JH,H = 4.3, 1 H, CH), 2.15 (s, 3 H, CH3CO), 1.85–1.78 (m, 1 H,
Methyl
(2R,3S)-2-({2-[(1S)-1-(methylthio)ethyl]phenyl}seleno)-5-
oxo-3,5-diphenylpentanoate and Methyl (2S,3R)-2-({2-[(1S)-1-
(methylthio)ethyl]phenyl}seleno)-5-oxo-3,5-diphenylpentanoate (4b):
Yield 13% (0.07 mmol, 33 mg), mixture of diastereoisomers 57:43,
2
3
CH2), 1.73–1.58 (m, 2 H, CH2), 1.42 (ddd, JH,H = 13.5, JH,H
=
8.9, 4.4 Hz, 1 H, CH2), 1.01 (s, 3 H, CH3), 0.92 (s, 3 H, CH3), 0.89
ppm (s, 3 H, CH3). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ
= 216.6, 205.3, 172.1, 143.0, 125.8, 125.3, 123.5, 57.4, 51.7, 47.6,
47.5, 46.8, 46.1, 44.4, 36.9, 29.8, 29.7, 22.7, 18.9, 18.7, 8.9 ppm.
MS (70 eV, EI): m/z (%): 456 (1) [M+], 425 (1), 225 (95), 193 (100),
183 (13), 153 (20), 137 (8), 123 (14), 109 (9), 83 (5), 69 (2), 55 (6).
Elemental analysis for C21H28O4SSe (455.5): calcd. C 55.38, H
6.20; found: C 55.25, H 6.26.
1
oil. H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 8.02–7.05 (m,
3
3
28 H, CH), 4.65 (q, JH,H = 7.0 Hz, 1 H, CH), 4.54 (q, JH,H
=
7.0 Hz, 1 H, CH), 4.24–3.90 (m, 6 H, CH, CH2), 3.62–3.40 (m, 2
H, CH2), 3.49 (s, 3 H, OCH3), 3.44 (s, 3 H, OCH3), 2.0 (s, 3 H,
3
SCH3), 1.99 (s, 3 H, SCH3), 1.64 (d, JH,H = 7.0 Hz, 3 H, CH3),
3
1.60 ppm (d, JH,H = 7.0 Hz, 3 H, CH3). 13C NMR (100 MHz,
CDCl3, 25 °C, TMS): δ = 198.6, 197.7, 172.0, 171.9, 146.0, 145.7,
141.1, 141.0, 136.9 (2C), 136.1, 135.6, 133.1 (2C), 130.8, 130.1,
129.1, 128.8, 128.7 (2C), 128.6 (2C), 128.5 (3C), 128.4 (3C), 128.1,
Methyl (2S,3R)-2-(Camphorseleno)-3-methyl-5-oxo-5-phenylpenta-
noate (3f) and Methyl (2S,3S)-2-(Camphorseleno)-3-methyl-5-oxo-5-
phenylpentanoate (4f): Yield 37% (0.18 mmol, 83 mg), mixture of 128.0 (3C), 127.9 (2C), 127.8, 127.7 127.5, 127.2, 127.0, 126.7, 52.0,
isomers syn:anti = 81:19, oil. syn isomer: 1H NMR (400 MHz,
51.9, 51.6 (2C), 44.1 (2C), 43.5, 43.3, 43.0, 42.7, 21.3, 21.2, 14.0,
548
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 543–551