2.95–3.1 (4H, m, ArCH2CH2, OH and ArCH(HЈ)CHR2),
3.22 (3H, m, CH2 and ArCH(HЈ)CHR2), 3.31 (2H, d, J < 2,
over 1 h and partitioned between aqueous HCl (0.5 M, 50 mL)
and ether–pentane 1:1 (40 mL). The organic layer was washed
with water (20 mL), NaHCO3 (aq., sat., 2 × 20 mL), NaCl (aq.,
sat., 2 × 20 mL), and dried (Na2SO4). Removal of the solvent
and column chromatography [light petroleum–CH2Cl2 (4:1)→
CH2Cl2 (100%)] afforded the title compound as an orange solid
(349 mg, 40%) which, when recrystallised (pentane–CH2Cl2
3:1, Ϫ25 ЊC), gave pink microcrystals: mp 105–107 ЊC; UV
(CH2Cl2) λmax/nm (log ε) 270(6.91), 308(6.35); δH (CDCl3, 300
MHz, J/Hz) 2.13 (2H, quintet, J 7.4, ArCH2CH2), 2.13 (2H,
quintet, J 7.5, ArCH2CH2), 2.77 (4H, br t, J 7.5, ArCH2CH2),
3.19 (2H, br t, J 7.3, ArCH2CH2), 2.84 (2H, t, J 7.6, ArCH2-
CH2), 3.00 [1H, dd, J1 2.6, J2 17.9, ArCH(HЈ)CHSePh], 3.47
[1H, dd, J1 7.6, J2 17.8, ArCH(HЈ)CHSePh], 4.21 (1H, dd,
J1 2.8, J2 7.7, ArCOCHSePh), 7.27–7.19 (3H, m, Ph), 7.62–7.57
(2H, m, Ph); δC (CDCl3, 75 MHz) 25.0, 25.4, all ArCH2CH2;
29.8, 30.4, 30.9, 31.9, all ArCH2CH2; 34.0, ArCH(HЈ)CHSePh;
44.4, ArCOCHSePh; 127.9, Ph; 128.5, Ar; 128.9, Ph; 129.7, C;
134.7, Ph; 136.8, 138.7, 140.4, 142.0, 146.3, 147.7, Ar; 203.6,
CO; MS m/z 369(11%), 368(32, Mϩ), 367(21), 287(25), 212(18),
211(100), 210(39) (Found: C 68.49; H 5.73. C21H20OSe requires
C, 68.66; H, 5.44%). A later fraction gave 2,3,4,5,6,7,8,9-octa-
hydro-2,2-bis(phenylselenyl)-1H-trinden-1-one as an orange oil
(187 mg, 15%): δH (CDCl3, 300 MHz, J/Hz) 2.00 (2H, quintet,
J 7.3, ArCH2CH2), 2.11 (2H, quintet, J 7.3, ArCH2CH2), 2.50
(2H, t, J 7.3, ArCH2CH2), 2.73 (4H, br t, J 7, ArCH2CH2), 3.15
(2H, t, J 7.3, ArCH2CH2), 3.23 [2H, s, ArCH2C(SePh)2], 7.20–
7.29 (6H, m, Ph), 7.59 (4H, m, Ph); δC (CDCl3, 75 MHz)
25.1, 25.4, all ArCH2CH2; 29.6, 30.4, 30.9, 31.9, all ArCH2CH2;
41.5, ArCH2C(SePh)2; 55.1, ArCOC(SePh)2; 127.9, Ar; 128.6,
Ph; 128.9, Ar; 129.0, Ph; 134.6, Ar; 136.8, Ph; 138.1, 140.5,
142.5, 143.5, Ar; 199.9, CO; MS m/z 522(2%), 368(9), 367(39):
366(30), 286(26), 279(15), 210(100). Also isolated was the
phenylselenyl-substituted “trindenone” 4,5,6,7,8,9-hexahydro-
2-phenylselenyl-1H-trinden-1-one as an orange oil (26 mg, 3%):
δH 2.0–2.3 (4H, m, ArCH2CH2), 2.67 (2H, m), 2.7–2.9 (4H, m),
2.99 (1H, t, J 7), 3.0–3.4 (2H, m), 7.23 (2H, m, Ph), 7.30 (1H, m,
Ph), 7.58 (2H, m, Ph); δC 25.3, 25.5, ArCH2CH2; 29.4, 30.2,
30.3, 31.4, ArCH2CH2; 128.1, 129.4, 130.9, Ar; 134.4, 134.4,
CH; 138.0, 141.1, 144.5, Ar; 144.5, CH; MS m/z 366(11%,
Mϩ), 279(22), 212(21), 211(56), 210(100). A small amount of
“trindenone” (14) was also isolated from the reaction products.
ArCH CH᎐C), 4.01 (1H, dd, J 8, J 13, ArCH CHR ), 5.17
᎐
2
1
2
2
2
(1H, d, J 5.4, ArCHOH), 6.49 (1H, t, J < 2, ArCH CH᎐C);
᎐
2
δC (CDCl3, 75 MHz) 25.4, 25.4, 25.6, 25.8, all ArCH2CH2;
30.5, 30.7, 30.9, 31.1, 31.2, 31.4, 31.4, 31.7, all ArCH2CH2;
34.4, ArCH CHR ; 36.6, ArCH CH᎐C; 46.0, ArCH CHR ;
᎐
2
2
2
2
2
74.4, ArCHOH; 130.7, ArCH CH᎐C; 134.3, 137.1, 137.3,
᎐
2
137.3, 137.5, 137.5, 137.8, 138.3, 139.0, 139.1, 139.3, 140.4,
143.4, Ar; MS m/z 410(1.5%), 409(9), 408(27, Mϩ), 391(37),
390(100), 213(30), 197(24), 196(6), 195(36); m/z found 408.2444
(Mϩ); C30H32O requires 408.2453.
Addition of aqueous HCl (0.5 mL, 2 M) to the mixed
alcohols above (20 mg in CH2Cl2, 2 mL) produced a two-phase
magenta solution containing the crude dehydrated title diene
(5) (10 mg, 52%, mp 170–175 ЊC), which was isolated by radial
chromatography following washing with Na2CO3 (5 mL, 2 M
aq.), distilled water (2 × 5 mL) and drying. Recrystallisation
(CH2Cl2–pentane) gave colourless needles that discoloured
on contact with air: mp 174–176 ЊC; UV (CH2Cl2) λmax/nm
(log ε) 276 (6.3), 308 (shoulder, 6.1); δH (CDCl3, 300 MHz,
J/Hz) 2.01 (2H, t, J 7.3, ArCH2CH2), 2.20–2.05 (6H, m, Ar-
CH2CH2), 2.94–2.78 (12H, m, ArCH2CH2), 3.00 (2H, t, J 7.1,
ArCH2CH2), 3.02 (2H, t, J 7.1, ArCH2CH2), 3.33 (2H, d, J < 2,
ArCH CH᎐C), 3.60 (2H, s, ArCH CR᎐C), 6.41 (1H, t, J 2.2,
᎐
᎐
2
2
ArCH CH᎐C), 6.91 (1H, s, ArCH᎐C); δ (CDCl3, 75 MHz)
᎐
᎐
2
C
25.5, 25.6, 25.7, 26.3, all ArCH2CH2; 29.7, 30.9, 31.3, 31.4, 31.9,
31.0, 31.0, 33.1, all ArCH CH ; 36.8, ArCH CH᎐C; 41.4,
᎐
2
2
2
ArCH CR᎐C; 128.1, ArCH᎐C; 130.9, ArCH CH᎐C; 134.5,
᎐
᎐
᎐
2
2
134.9, 135.7, 136.4, 136.9, 137.1, 137.4, 138.1, 138.4, 139.2,
139.2, 139.4, 142.4, 143.0, vinylic and Ar; MS m/z 392(4.4%),
391(29), 390(88, Mϩ), 196(28), 195(66), 44(100); m/z found
390.2345 (Mϩ); C30H30 requires 390.2347.
4aRS,4bRS,7aSR,7bRS-1,2,3,4,4a,4b,7a,7b,8,9,10,11,12,13,14,
15,16,17-octadecahydro-6-oxabis(as-indaceno)[4,5-a:4Ј,5Ј-f]-
trindene-5,7-dione (8)
Diene (5) (2.7 mg, 0.0069 mmol) and maleic anhydride (2.2 mg,
0.022 mmol, 3.3 mol equiv.) in toluene (1.2 mL) were heated
under reflux under nitogen and the reaction was monitored
by TLC (CH2Cl2). After 4.5 h, chromatography on silica
gel (CH2Cl2) afforded the cycloaddition adduct 8 as a white
solid (2.5 mg, 74%) which upon recrystallisation (CH2Cl2–
toluene) gave colourless needles (0.9 mg, 27%): mp 285–295 ЊC;
δH (CDCl3, 300 MHz, J/Hz) 2.0–2.2 (8H, m, ArCH2CH2), 2.75–
2.95 (14H, m, ArCH2CH2), 3.0–3.2 (2H, m, CH2), 3.35–3.5 (2H,
m), 3.60–3.66 (3H, m), 3.93 (1H, dt, J1 9.2, J2 9.0, ArCH2-
CHRCHR2), 4.02 (1H, br d, J 9, ArCHRCHR2), 4.09 (1H, br d,
J 9, ArCHRCHR2); δC (CDCl3, 75 MHz) 25.1, 25.3, 25.3,
25.6, ArCH2CH2; 29.7, 30.6, 31.0, 31.0, 31.2, 31.4, 31.5, 31.6,
ArCH2CH2; 34.7, 37.2, ArCH2; 41.7, 42.8, 44.0, 48.9, CH;
130.8, 132.7, 136.1, 138.0, 138.2, 138.7, 139.7, 139.8, 139.3,
141.1, 141.3, 144.5, 145.0, 148.1, vinylic and Ar; 170.0, 172.0,
CO; MS 490 (1.2%), 489 (6.6), 488 (17.4, Mϩ), 460 (23.0), 390
(100), 195 (46.9); m/z found 488.2353 (Mϩ); C34H32O3 requires
488.2352.
4,5,6,7,8,9-Hexahydro-1H-trinden-1-one (14)
(2RS)-2,3,4,5,6,7,8,9-Octahydro-2-phenylselenyl-1H-trinden-1-
one (49.0 mg, 0.133 mmol) was dissolved in CH2Cl2–Et3N
(2 mL, 19:1) and H2O2 (1 mL, 27% aq.) was added slowly
with vigorous stirring until reaction was complete (5 min).
The organic layer was washed with water (2 mL) and dried
(Na2SO4). Radial chromatography gave “trindenone” (14)
(8.8 mg, 31%) as orange prisms: mp 87–88 ЊC (decomp.); UV
(CH2Cl2) λmax/nm (log ε) 248(sh., 4.4), 252(4.5), 354(3.6);
δH (CDCl3, 300 MHz, J/Hz) 2.12 (2H, quintet, J 7.3, ArCH2-
CH2), 2.12 (2H, quintet, J 7.3, ArCH2CH2), 2.68–2.86 (6H,
m, ArCH2CH2), 3.04 (2H, t, J 7.4, ArCH2CH2), 5.75 (1H, d,
J 6.1, ArCOCH᎐CHAr or ArCOCH᎐CHAr), 7.52 (1H, d, J 6.1,
᎐
᎐
ArCOCH᎐CHAr or ArCOCH᎐CHAr); δ (CDCl3, 75 MHz)
᎐
᎐
C
(2RS)-2,3,4,5,6,7,8,9-Octahydro-2-phenylselenyl-1H-trinden-1-
one
25.4, 25.5, all ArCH2CH2; 29.4, 30.17, 30.22, 31.4, all ArCH2-
CH ; 123.4, Ar; 126.1, ArCOCH᎐CHAr or ArCOCH᎐CHAr;
᎐
᎐
2
137.0, 137.8, 141.8, 142.2, 145.9, Ar; 147.7, ArCOCH᎐CHAr or
᎐
A solution of lithium diisopropylamide (LDA) was freshly pre-
pared by the dropwise addition of n-BuLi (1.10 mL, 2.5 M in
hexanes, 2.75 mmol) to a stirred solution of diisopropylamine
(0.42 mL, 2.72 mmol) in dried THF (3 mL) under nitrogen
at Ϫ70 ЊC. The LDA (1.2 mol equiv.) was transferred drop-
wise through a cannula to a continuously stirred solution of
trindanone 2 (502 mg, 2.37 mmol) in dried THF (51 mL) also
at Ϫ70 ЊC. After 30 min a solution of benzeneselenenyl chloride
(0.68 g, 1.5 mol equiv. in THF, 6 mL) was rapidly added and the
reaction mixture was allowed to warm to room temperature
ArCOCH᎐CHAr; 199.9, CO; MS m/z 211(17%), 210(100, Mϩ),
᎐
209(33), 195(9), 182(29), 165(26), 153(21), 152(23) (Found:
C, 85.21; H, 6.99. C15H14O requires C, 85.68; H, 6.66%).
(6cSR,6dRS,13aSR,13bRS)-1,2,3,4,5,6,6c,6d,7,8,9,10,11,12,
13a,13b,14,15,16,17,18,19,20,21-Tetracosahydrotris(as-
indaceno)[4,5-a:4Ј,5Ј-f :4Љ,5Љ-l]trinden-13-one (19)
A solution of diene 5 (16.3 mg, 0.042 mmol) and “trindenone”
(14) (9.8 mg, 0.047 mmol) in PhCl (3 mL) was heated under
3510
J. Chem. Soc., Perkin Trans. 1, 2000, 3505–3512