SPECIAL TOPIC
Sulfinyl Homo- and Hetero-Dienes from Sulfenic Acids
2247
MS: m/z (%) = 375 (25) (M + 1), 154 (48), 136 (60), 107 (45), 91
(71), 77 (79), 55 (100).
13C NMR: = 155.93 (C-4), 118.63 (4 = CH2), 102.06 (C-3), 85.09
(C-1), 63.46 (OCH2), 57.90 (C-6), 52.99 (C-7), 47.85 (C-12), 44.65
(C-10), 38.80 (C-11), 32.99 and 26.94 (C-8,9), 20.68 and 20.16 (C-
13,14), 14.84 (CH2CH3).
Anal. Calcd for C21H30N2O2S: C, 67.34; H, 8.07; N, 7.48. Found: C,
67.39; H, 8.04; N, 7.50.
MS: m/z (%) = 285 (59) (M + 1), 135 (52), 95 (54), 81 (62), 69 (79),
Thermolysis of (1S)-10-[(2-Cyanoethyl)sulfinyl]isoborneols 9 in
the Presence of Propiolaldehyde Diethyl Acetal (22); Typical
Procedure
55 (100).
Anal. Calcd for C15H24O3S: C, 63.35; H, 8.51. Found: C, 63.39; H,
8.47.
Sulfoxides 9 (mixture of sulfur epimers,2 0.66 g, 2.7 mmol) in tolu-
ene (5 mL) containing commercial acetal 22 (1.00 g, 7.8 mmol)
were maintained at reflux temperature. When the reaction appeared
complete by TLC (after ca 3 h) the solvent was removed under re-
duced pressure. The column chromatography of the crude product
mixture, eluted with petrol containing 10–50% EtOAc, afforded the
sulfoxides 23–25 (23/24/25 in a 47:30:23 ratio, 65% total yield),
which eluted in the order given.
Thermolysis of (1S)-10-[(2-Cyanoethyl)sulfinyl]isoborneols 9 in
the Presence of 4-Phenyl-3-butyn-2-one (30); Typical Proce-
dure
Sulfoxides 9 (mixture of sulfur epimers,2 0.37 g, 1.4 mmol) in tolu-
ene (4 mL) containing commercial butynone 30 (0.30 g, 2.1 mmol)
were maintained at reflux temperature. When the reaction appeared
complete by TLC (after ca 3.5 h) the solvent was removed under re-
duced pressure. The column chromatography of the crude product
mixture, eluted with petrol containing 7–20% EtOAc, afforded the
sulfur epimers 31 and 32 (31/32 in a 61:39 ratio, 70% total yield),
which eluted in the order given.
(RS)-3,3-diethoxy-2-[(1S)-isoborneol-10-sulfinyl]propene (23)
Oil; [ ]D22 +0.6 (c 6.2).
1H NMR: = 6.18 (br s, 1 H, H-1 cis to SO), 6.01 (br s, 1 H, H-1
trans to SO), 5.24 (t, 1 H, J1,3 = 0.9 Hz, H-3), 4.11 (dd, 1 H, J2 ,3
=
8.0, 4.2 Hz, H-2 ), 3.7–3.5 (m, 4 H, OCH2), 3.08 and 3.02 (AB sys-
tem, 2 H, J10 A,10 B = 13.2 Hz, H2-10 ), 1.9–1.6 (m, 7 H, H2-3 ,5 ,6 ,
H-4 ), 1.25 (m, 6 H, CH2CH3), 1.07 (s, 3 H, H3-8 ), 0.83 (s, 3 H, H3-
9 ).
13C NMR: = 151.65 (C-2), 119.17 (C-1), 99.60 (C-3), 76.85 (C-
2 ), 62.41 and 62.19 (OCH2), 56.39 (C-10 ), 51.62 (C-1 ), 48.05 (C-
7 ), 44.96 (C-4 ), 38.28 (C-3 ), 30.50 and 27.00 (C-5 ,6 ), 20.25 and
19.70 (C-8 ,9 ), 14.85 (CH2CH3).
(RS,E)-4-[(1S)-isoborneol-10-sulfinyl]-4-phenyl-3-buten-2-one
(31)
Oil; [ ]D25 +51.5 (c 0.1).
1H NMR: = 7.5–7.3 (m, 5 H, Ph), 6.87 (s, 1 H, H-3), 4.11 (dd, 1
H, J2 ,3 = 8.0, 4.3 Hz, H-2 ), 3.00 and 2.23 (AB system, 2 H,
J
10 A,10 B = 13.2 Hz, H2-10 ), 2.15 (s, 3 H, H3-1), 1.8–1.0 (m, 7 H, H2-
3 ,5 ,6 , H-4 ), 1.00 (s, 3 H, H3-8 ), 0.56 (s, 3 H, H3-9 ).
13C NMR: = 197.69 (C-2), 157.33 (C-4), 130.89 (C-1 ), 130.43
(C-3), 129.27 (C-3 ,5 ), 128.12 (C-2 ,6 ), 128.05 (C-4 ), 76.89
(C-2 ), 54.12 (C-10 ), 51.36 (C-1 ), 48.24 (C-7 ), 44.96 (C-4 ), 38.43
(C-3 ), 31.00 (C-1), 30.63 and 26.97 (C-5 ,6 ), 20.21 and 19.69 (C-
8 ,9 ).
MS: m/z (%) = 331 (16) (M + 1), 285 (57) (M + 1 – C2H6O), 239
(15), 135 (99), 69 (78), 55 (100), 43 (81).
Anal. Calcd for C17H30O4S: C, 61.78; H, 9.15. Found: C, 61.96; H,
9.12.
Anal. Calcd for C20H26O3S: C, 69.33; H, 7.56. Found: C, 69.45; H,
7.59.
(SS)-3,3-Diethoxy-2-[(1S)-isoborneol-10-sulfinyl]propene (24)
Oil; [ ]D22 +23.3 (c 3.0).
(SS,E)-4-[(1S)-Isoborneol-10-sulfinyl]-4-phenyl-3-buten-2-one
(32)
Oil.
IR (nujol): 3384 (OH), 1726, 1288, 1117, 1074, 1059 (SO), 940
cm–1.
1H NMR: = 6.18 (d, 1 H, J1,3 = 0.9 Hz, H-1 cis to SO), 6.03 (d, 1
H, J1,3 = 1.1 Hz, H-1 trans to SO), 5.27 (t, 1 H, H-3), 4.08 (dd, 1 H,
J2 ,3 = 7.4 and 4.1 Hz, H-2 ), 3.7–3.5 (m, 4 H, OCH2), 3.73 and 2.48
(AB system, 2 H, J10 A,10 B = 14.2 Hz, H2-10 ), 1.8–1.4 (m, 7 H, H2-
3 ,5 ,6 , H-4 ), 1.26 (m, 6 H, CH2CH3), 1.09 (s, 3 H, H3-8 ), 0.84 (s,
3 H, H3-9 ).
13C NMR: = 151.26 (C-2), 120.27 (C-1), 99.99 (C-3), 76.90 (C-
2 ), 62.98 and 61.82 (OCH2), 55.62 (C-10 ), 51.87 (C-1 ), 48.42 (C-
7 ), 44.68 (C-4 ), 39.29 (C-3 ), 30.55 and 27.35 (C-5 ,6 ), 20.40 and
19.88 (C-8 ,9 ), 14.72 (CH2CH3).
1H NMR: = 7.5–7.3 (m, 5 H, Ph), 6.88 (s, 1 H, H-3), 4.02 (t, 1 H,
J2 ,3 = 5.8 Hz, H-2 ), 3.16 and 2.30 (AB system, 2 H, J10 A,10 B = 13.9
Hz, H2-10 ), 2.15 (s, 3 H, H3-1), 1.8–1.0 (m, 7 H, H2-3 ,5 ,6 , H-4 ),
0.92 (s, 3 H, H3-8 ), 0.66 (s, 3 H, H3-9 ).
13C NMR: = 197.91 (C-2), 157.27 (C-4), 131.14 (C-1 ), 130.43
(C-3), 129.19 (C-3 ,5 ), 128.45 (C-2 ,6 ), 128.41 (C-4 ), 76.53
(C-2 ), 52.42 and 52.11 (C-1 ,10 ), 48.80 (C-7 ), 44.54 (C-4 ), 39.96
(C-3 ), 31.17 and 27.30 (C-5 ,6 ), 30.87 (C-1), 20.25 and 19.99 (C-
8 ,9 ).
Anal. Calcd for C20H26O3S: C, 69.33; H, 7.56. Found: C, 69.15; H,
7.54.
MS: m/z (%) = 285 (19) (M + 1 – C2H6O), 239 (36), 135 (100), 69
(78), 55 (96), 43 (69).
Anal. Calcd for C17H30O4S: C, 61.78; H, 9.15. Found: C, 61.66; H,
9.14.
(4R,4aR,7aS,RS)-4,6-Dimethyl-1-dimethylamino-3-[(1S)-iso-
borneol-10-sulfinyl]-4,4a,6,7a-tetrahydro-1H-pyrrolo[3,4-b]py-
ridine-5,7-dione (29)
A solution of azadiene 6 (0.03 g, 0.1 mmol) and N-methylmaleim-
ide (0.02 g, 0.2 mmol) in 1,2-dichloroethane (3 mL) was refluxed
under stirring. When the reaction appeared complete by TLC (after
4 days) the solvent was removed under reduced pressure. Purifica-
tion by column chromatography eluting with petrol–EtOAc (60:40)
afforded the adduct 29 as an oil (20% yield).
1H NMR: = 6.94 (s, 1 H, H-2), 4.24 (d, 1 H, J4a,7a = 8.0 Hz, H-7a),
4.06 (dd, 1 H, J2 ,3 = 7.4, 3.4 Hz, H-2 ), 3.76 and 2.08 (AB system,
2 H, J10 A,10 B = 13.2 Hz, H2-10 ), 3.41 (dq, 1 H, J4,4a = 3.4, J4,Me = 6.9
Hz, H-4), 2.61 (s, 6 H, NMe2), 3.08 (dd, 1 H, H-4a), 3.00 (s, 3 H, 6-
(1R,3S,7S,10R,RS)-3-Ethoxy-4-methylene-2-oxa-5-thiatricy-
clo[5.4.0.17,10]dodecane 5-Oxide (25)
Oil.
IR (nujol): 1725, 1178, 1113, 1072, 1048 (SO), 943 cm–1.
1H NMR: = 6.03 and 5.89 (2 × br s, 2 H, 4=CH2), 5.24 (t, 1 H,
Jlong-range = 1.2 Hz, H-3), 3.85 and 3.56 (16 lines, 2 H, Jgem = 9.4,
Jvic = 7.1 Hz, OCH2), 3.71 (dd, 1 H, J1,11 = 8.3, 3.7 Hz, H-1), 3.10
and 2.95 (AB system, 2 H, J6A,6B = 13.5 Hz, H2-6), 2.0–1.4 (m, 7 H,
H2-8,9,11, H-10), 1.26 (t, 3 H, CH2CH3), 1.20 (s, 3 H, H3-13), 0.96
(s, 3 H, H3-14).
Synthesis 2003, No. 14, 2241–2248 © Thieme Stuttgart · New York