R. A. Novikov et al. / Tetrahedron Letters 52 (2011) 4996–4999
4999
21. General procedure for the synthesis of tetralines 8a–g: To
a
solution of
the Division of Chemistry and Materials Science of the Russian
Academy of Sciences (Program for Basic research ‘‘Theoretical and
Experimental Study of the Nature of Chemical Bonds and Mecha-
nisms of Important Chemical Reactions and Processes’’).
cyclopropane 1 (100 mg, 0.43 mmol) in dry CH2Cl2 (concentration indicated
in Table 1 and Fig. 2) under an argon atmosphere was added a solution of
SnCl4ꢀTHF (284 mg, 0.85 mmol) in CH2Cl2 (0.5 mL) and mixture was stirred at a
room temperature for 12 h. Next, an aqueous solution of HCl (5%) was added at
0 °C until pH 3 was achieved and the reaction mixture was extracted with
CH2Cl2 (3 ꢃ 10 mL). The organic layer was dried over MgSO4 and the solvent
was removed in vacuo. The residue was separated by column chromatography
on silica gel (benzene–EtOAc, 20:1 to pure EtOAc) to afford individual
compounds 8a–g as a colorless oil or solid (mixture of diastereomers). The
References and notes
1. Reissig, H. U.; Zimmer, R. Chem. Rev. 2003, 103, 1151.
2. (a) Beal, R. B.; Dombroski, M. A.; Snider, B. B. J. Org. Chem. 1986, 51, 4391; (b)
Shimada, S.; Hashimoto, Y.; Sudo, A.; Hasegawa, M.; Saigo, K. J. Org. Chem. 1992,
57, 7126.
3. (a) Yadav, V. K.; Sriramurthy, V. Org. Lett. 2004, 6, 4495; (b) Yadav, V. K.;
Sriramurthy, V. Angew. Chem. 2004, 116, 2723.
4. (a) Pohlhaus, P. D.; Johnson, J. S. J. Org. Chem. 2005, 70, 1057; (b) Min, S.; Yang,
Y. H.; Bo, X. Tetrahedron 2005, 61, 1893; (c) Bernard, A. M.; Frongia, A.; Piras, P.
P.; Secci, F.; Spiga, M. Org. Lett. 2005, 7, 4565.
products obtained could be additionally separated on
a
Silufol
chromatographic plate (20 ꢃ 20 cm) to afford the pure diastereomers.
Spectral data for selected compounds:
(1R⁄,4R⁄)-dimethyl-1-(2,2-bismethoxycarbonyl-1-ethyl)-4-phenyl-1,2,3,4-tetra-
hydronaphthalen-2,2-dicarboxylate (8a): Colorless thick oil. IR (CHCl3):
m 3056,
2987, 2955, 1734 br (C@O), 1602, 1550, 1495, 1434, 1422 cmꢁ1 1H NMR
.
(400.1 MHz, CDCl3): d 2.03–2.23 (m, 2H, Ha,b(10)), 2.67 (ddd, 1H, Ha(3), 2J = 14.9,
3J = 4.3, 4J = 1.2 Hz), 2.98 (dd, 1H, Hb(3), 2J = 14.9, 3J = 8.9 Hz), 3.19 (s, 3H, OCH3),
3.43–3.55 (m, 2H, H(1) and H(20)), 3.61, 3.75 and 3.82 (all s, 3 ꢃ 3H, 3OCH3),
4.36 (dd, 1H, H(4), 3J = 8.9 and 4.3 Hz), 6.82 (m, 1H, H(5)), 7.01 (m, 2H, o-Ph),
7.04–7.34 (m, 6H, H(6), H(7), H(8), m-Ph and p-Ph). 13C NMR (100.6 MHz,
CDCl3): d 31.5 (C(10)), 33.5 (C(3)), 41.6 (C(4)), 41.8 (C(1)), 49.9 (C(20)), 52.2,
52.6, 52.8 and 52.9 (4OCH3), 56.9 (C(2)), 126.3, 126.5, 127.0 and 129.1 (C(6),
C(7), C(8) and p-C), 128.1 (2m-C), 129.2 (2o-C), 130.2 (C(5)), 136.7 (C(4a)),
137.6 (C(8a)), 145.9 (i-C), 169.4, 169.6, 170.7 and 170.9 (4COO). MS (m/z, %):
468 (19, M+), 437 (7, M+–OCH3), 405 (7), 376 (21), 358 (12), 336 (16), 324 (38),
317 (35), 277 (58), 263 (41), 244 (37), 231 (63), 217 (67), 203 (66), 191 (22),
178 (34), 165 (16), 145 (61), 121 (71), 115 (54), 104 (23), 91 (48), 77 (29), 59
(100), 55 (44). HRMS calcd for C26H28O8: [M+Na]+, 491.1676. Found: m/z
491.1672.
5. Graziano, M. L.; Iesce, M. R. J. Chem. Res. 1987, 362.
6. (a) Carson, C. A.; Kerr, M. A. J. Org. Chem. 2005, 70, 8242; (b) Wurz, R. P.;
Charette, A. B. Org. Lett. 2005, 7, 2313; (c) Saigo, K.; Shimada, S.; Hasegawa, M.
Chem. Lett. 1990, 905.
7. (a)Graziano,M.L.;Iesce,M.R.;Cermola,F.J.Chem.Res.1996,82;(b)Korotkov,V.S.;
Larionov,O.V.;Hofmeister,A.;Magull,J.;deMeijere,A.J.Org.Chem.2007,72,7504.
8. (a) Yu, M.; Pagenkopf, B. L. Org. Lett. 2001, 3, 2563; (b) Yu, M.; Pagenkopf, B. L. J.
Am. Chem. Soc. 2003, 125, 2563.
9. Liu, L.; Montgomery, J. J. Org. Lett. 2007, 9, 3885.
10. Tomilov, Y. V.; Novikov, R. A.; Nefedov, O. M. Tetrahedron 2010, 66, 9151.
11. Perreault, C.; Goudreau, S. R.; Zimmer, L. E.; Charette, A. B. Org. Lett. 2008, 10,
689.
12. (a) Cardona, F.; Goti, A. Angew. Chem. 2005, 117, 8042; (b) Sibi, M. P.; Ma, Z. H.;
Jasperse, C. P. J. Am. Chem. Soc. 2005, 127, 5764; (c) Ganton, M. D.; Kerr, M. A. J.
Org. Chem. 2004, 69, 8554.
(1R⁄,4S⁄)-8a: Colorless thick oil. IR (CHCl3):
1603, 1550, 1495, 1434, 1421 cmꢁ1
m
3055, 2986, 2955, 1734 br (C@O),
.
1H NMR (400.1 MHz, CDCl3): d 2.03–2.23
(m, 2H, Ha,b(10)), 2.38 (dd, 1H, Ha(3), 2J = 14.5, 3J = 11.7 Hz), 2.79 (ddd, 1H,
Hb(3), 2J = 14.5, 3J = 7.3, 4J = 1.7 Hz), 3.49 (m, 1H, H(20)), 3.63 (m, 1H, H(1)), 3.64,
3.66, 3.80 and 3.84 (all s, 4 ꢃ 3H, 4OCH3), 3.98 (dd, 1H, H(4), 3J = 11.7 and
7.3 Hz), 6.82 (m, 1H, H(5)), 7.01 (m, 2H, o-Ph), 7.04–7.34 (m, 6H, H(6), H(7),
13. England, D. B.; Kuss, T. D. O.; Keddy, R. G.; Kerr, M. A. J. Org. Chem. 2001, 66,
4704.
14. Chagarovskiy, A. O.; Ivanova, O. A.; Rakhmankulov, E. R.; Budynina, E. M.;
Trushkov, I. V.; Melnikov, M. Y. Adv. Synth. Catal. 2010, 352, 3179.
15. (a)Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1353;(b)Pohlhaus, P. D.;
Sanders, S. D.; Parsons, A. T.; Li, W.;Johnson, J. S. J. Am. Chem. Soc. 2008, 130, 8642.
16. Mume, E.; Munslow, I. J.; Kaellstroem, K.; Andersson, P. G. Collect. Czech. Chem.
Commun. 2007, 72, 1005.
17. Nair, V.; Jessy, M. J. Chem. Soc., Perkin Trans. 1 1995, 1881.
18. Martelli, J.; Gree, R. J. Chem. Soc., Chem. Commun. 1980, 355.
19. Dimethyl-2-(1,3-dimethoxy-1,3-dioxopropan-2-yl)-3,4-diphenylcyclopentane-1,1-
dicarboxylate (7): To a solution of cyclopropane 1 (200 mg, 0.85 mmol) in dry
CH2Cl2 (5 mL) under an argon atmosphere was added a solution of GaCl3
(30 mg, 0.17 mmol) in CH2Cl2 (0.5 mL) and the mixture was stirred at a room
temperature for 30 min. Next, an aqueous solution of HCl (5%) was added at
0 °C until pH 3 was achieved and the reaction mixture was extracted with
CH2Cl2 (3 ꢃ 10 mL). The organic layer was dried over MgSO4 and the solvent
was removed in vacuo. The residue was purified by column chromatography
on silica gel (benzene–EtOAc, 20:1) to afford compound 7 (145 mg, 73%) as a
colorless oil (ca. 2:1 mixture of diastereomers). The product obtained can be
additionally separated on a Silufol chromatographic plate (20 ꢃ 20 cm) eluting
with benzene–EtOAc, 10:1 to afford the pure isomers.
13
H(8), m-Ph and p-Ph). C NMR (100.6 MHz, CDCl3): d 33.3 (C(3)), 33.8 (C(10)),
40.9 (C(1)), 43.5 (C(4)), 49.6 (C(20)), 52.71, 52.80, 52.89 and 52.92 (4OCH3),
58.7.9 (C(2)), 126.3, 126.7, 127.1 and 129.4 (C(6), C(7), C(8) and p-C), 128.7 (2o-
C), 128.8 (2m-C), 130.5 (C(5)), 136.9 (C(4a)), 137.8 (C(8a)), 146.1 (i-C), 169.4,
169.6, 170.3 and 170.4 (4COO). HRMS calcd for C26H28O8: [M+Na]+, 491.1676.
Found: m/z 491.1673.
(1R⁄,4R⁄)-dimethyl-1-[(3R⁄)-2,2,5,5-tetramethoxycarbonyl-3-phenyl-1-pentyl]-4-
phenyl-1,2,3,4-tetrahydronaphthalen-2,2-dicarboxylate (8b): Colorless thick oil.
IR (CHCl3):
m 3055, 2987, 2956, 1735 br (C@O), 1602, 1550, 1495, 1435, 1422
cmꢁ1
.
1H NMR (400.1 MHz, CDCl3): d 2.05 (dd, 1H, Ha(10), 2J = 14.3, 3J = 2.8 Hz),
2.21–2.37 (m, 2H, Hb(10) and Ha(40)), 2.61 (ddd, 1H, Ha(3), 2J = 15.1, 3J = 6.9,
4J = 2.4 Hz), 2.62 (m, 1H, Hb(40)), 2.85 (dd, 1H, Hb(3), 2J = 15.1, 3J = 9.8 Hz), 3.00
(dd, 1H, H(50), 3J = 10.4 and 4.3 Hz), 3.27 and 3.32 (all s, 2 ꢃ 3H, 2OCH3), 3.44
(dd, 1H, H(3), 3J = 12.0 and 2.3 Hz), 3.52, 3.53, 3.57 and 3.78 (all s, 4 ꢃ 3H,
´
4OCH3), 3.80 (m, 1H, H(1)), 4.02 (dd, 1H, H(4), 3J = 9.8 and 6.9 Hz), 6.50 (m, 1H,
H(5)), 6.95 (m, 1H, H(6)), 7.03–7.25 (m, 12H, H(7), H(8) and 2Ph). 13C NMR
(100.6 MHz, CDCl3): d 31.9 (C(40)), 34.0 (C(10)), 34.3 (C(3)), 41.8 (C(1) and C(4)),
49.2 (C(30)), 50.4 (C(50)), 51.8, 52.2, 52.4, 52.52, 52.55 and 52.8 (6OCH3), 59.1
´
(C(2)), 60.7 (C(2)), 125.8 (C(7)), 126.6 (p-C, Ph at C(4)), 127.0 (C(6)), 127.7
Anti,syn-7: Colorless thick oil. IR (CHCl3):
m 3055, 2987, 2955, 1735 br (C@O),
(C(5)), 127.9, 128.4, 128.56, 128.58, 129.5 and 129.9 (C(8), 2Ph), 137.0 (i-C, Ph
at C(30)), 137.5 (C(4a)), 139.4 (C(8a)), 144.9 (i-C, Ph at C(4)), 169.4, 169.5, 169.7,
170.1, 170.6 and 170.9 (6COO). HRMS calcd for C39H42O12: [M+Na]+, 725.2568.
Found:⁄m/z⁄725.2558.
1603, 1550, 1495, 1436, 1423 cmꢁ1 1H NMR (400.1 MHz, CDCl3): d 2.56 (m, 1H,
.
H
anti(5)), 3.02 (m, 1H, Hsyn(5)), 3.05 (m, 1H, H(4)), 3.22 and 3.47 (all s, 2 ꢃ 3H,
2OCH3), 3.61 (m, 1H, H(3)), 3.72 and 3.85 (all s, 2 ꢃ 3H, 2OCH3), 3.90 (d, 1H,
H(20), 3J = 5.9 Hz), 4.06 (dd, 1H, H(2), 3J = 10.4 and 5.9 Hz), 7.04–7.20 (m, 10H, 2
(1R⁄,4S ,30S )-8b: Colorless thick oil. IR (CHCl3):
m 3055, 2987, 2955, 1734 br
13
(C@O), 1602, 1550, 1494, 1436, 1422 cmꢁ1 1H NMR (400.1 MHz, CDCl3): d 1.80
.
Ph). C NMR (100.6 MHz, CDCl3): d 42.2 (C(5)), 49.8 (C(2)), 51.8 (C(20)), 52.0,
(dd, 1H, Ha(10), 2J = 13.8, 3J = 1.7 Hz), 2.08 (dd, 1H, Ha(3), 2J = 14.7, 3J = 10.9 Hz),
2.18 (dd, 1H, Hb(10), 2J = 13.8, 3J = 11.5 Hz), 2.42 (m, 2H, Ha,b(40)), 2.77 (ddd, 1H,
Hb(3), 2J = 14.7, 3J = 8.8, 4J = 1.8 Hz), 2.93 (s, 3H, OCH3), 3.01 (m, 1H, H(50)), 3.30
(m, 1H, H(30)), 3.52 and 3.54 (all s, 2 ꢃ 3H, 2OCH3), 3.57 (dd, 1H, H(1), 3J = 11.5
and 1.7 Hz), 3.72, 3.77 and 3.92 (all s, 3 ꢃ 3H, 3OCH3), 3.98 (dd, 1H, H(4),
3J = 10.9 and 8.6 Hz), 6.67 (m, 1H, H(5)), 6.83 (m, 2H, o-Ph at C(4)), 6.92 (m, 1H,
H(6)), 6.97 (m, 2H, o-Ph at C(30)), 7.02 (m, 1H, H(7)), 7.07–7.17 (m, 5H, H(8), m-
Ph at C(4), p-Ph at C(4) and p-Ph at C(30)), 7.23 (m, 2H, m-Ph at C(30)). 13C NMR
(100.6 MHz, CDCl3): d 30.7 (C(40)), 33.3 (C(3)), 40.7 (C(1)), 41.2 (C(10)), 43.2
(C(4)), 50.3 (C(50)), 51.2 (OCH3), 52.1 (C(30)), 52.50, 52.520, 52.522, 52.8 and
52.9 (5OCH3), 60.0 (C(2)), 61.5 (C(20)), 125.7 (C(7)), 126.2 (p-C, Ph at C(4)),
126.8 (C(6)), 128.1 (p-C, Ph at C(30)), 128.3 (2m-C, Ph at C(30)), 128.4 (2o-C, Ph
at C(4)), 128.7 (2m-C, Ph at C(4)), 129.7 (C(5) and 2o-C, Ph at C(30)), 130.2
(C(5)), 136.3 (i-C, Ph at C(30)), 136.7 (C(4a)), 138.3 (C(8a)), 147.1 (i-C, Ph at
C(4)), 168.1, 169.3, 169.5, 170.0, 170.5 and 170.6 (6COO). HRMS calcd for
52.1, 52.7 and 53.3 (4OCH3), 52.9 (C(4)), 55.7 (C(3)), 61.6 (C(1)), 126.66 and
126.68 (2 p-C), 127.6, 128.1, 128.3 and 128.6 (2 ꢃ 2 o-C and 2 ꢃ 2 m-C), 140.6
and 140.7 (2 i-C), 168.5, 168.6, 170.8 and 172.9 (4COO). MS (m/z, %): 468 (2,
M+), 437 (1, M+–OCH3), 376 (2), 336 (27), 276 (36), 245 (15), 217 (25), 203 (20),
171 (21), 145 (24), 115 (88), 91 (64), 77 (32), 59 (100), 51 (24), 39 (14). HRMS
calcd for C26H28O8: [M+H]+, 469.1857; [M+Na]+, 491.1676; [M+K]+, 507.1416.
Found: m/z 469.1648, 491.1673, 507.1425.
Anti,anti-7: Colorless thick oil. IR (CHCl3):
1602, 1550, 1496, 1435, 1423 cmꢁ1 1H NMR (400.1 MHz, CDCl3): d 2.69 (m, 1H,
syn(5)), 2.86 (m, 1H, Hanti(5)), 3.25, 3.43, 3.76 and 3.86 (all s, 4 ꢃ 3H, 4OCH3),
m 3055, 2988, 2955, 1735 br (C@O),
.
H
3.83 (m, 2H, H(3) and H(4)), 3.96 (m, 1H, H(2)), 4.18 (d, 1H, H(20), 3J = 7.3 Hz),
6.80–7.03 (m, 10H, 2Ph). 13C NMR (100.6 MHz, CDCl3): d 39.7 (C(5)), 48.1
(C(4)), 51.1 (C(2)), 51.4 (C(3)), 51.9, 52.3, 52.6 and 53.1 (4OCH3), 52.8 (C(20)),
61.9 (C(1)), 126.0 and 126.1 (2 p-C), 127.5, 127.6, 128.4 and 129.3 (2 ꢃ 2 o-C
and 2 ꢃ 2 m-C), 139.8 and 141.0 (2 i-C), 168.5, 169.1, 170.8 and 172.2 (4COO).
MS (m/z, %): 468 (1, M+), 437 (1, M+–OCH3), 376 (2), 336 (24), 276 (33), 245
(16), 217 (25), 203 (218), 171 (23), 145 (25), 115 (89), 91 (59), 77 (33), 59
(100), 51 (28), 39 (20). HRMS calcd for C26H28O8: [M+H]+, 469.1857; [M+Na]+,
491.1676; [M+K]+, 507.1416. Found: m/z 469.1649, 491.1672, 507.1423.
20. The first example of the formation of substituted tetralins via dimerization of
dimethyl 2-arylcyclopropandicarboxylates in the presence of Lewis acids was
described by Ivanova, O. A.; Budynina, E. M.;Chagarovskiy, A. O.; Trushkov, I. V. at
theInternationalSymposiumonAdvancedSciencesinOrganicChemistry(ASOC-
10), Miskhor, Crimea, June 2010. Abstracts (ChemBridge), U-24 (inRussian).
C
39H42O12: [M+Na]+, 725.2568. Found: m/z 725.2560.
Tetramer 8c: Colorless solid, mp 88–89 °C. ESI-MS (m/z): 959.3 [M+Na]+. HRMS
calcd for C52H56O16: [M+H]+, 937.3641; [M+Na]+, 959.3461; [M+K]+, 975.3200.
Found: m/z 937.3655, 959.3463, 975.3240.
Pentamer 8d: ESI-MS (m/z): 1193.3 [M+Na]+. HRMS calcd for C65H70O20
:
[M+Na]+, 1193.4353. Found: m/z 1193.4349.
Hexamer 8e: ESI-MS (m/z): 1427.5 [M+Na]+ calcd for C78H84O24
.
Heptamer 8f: ESI-MS (m/z): 1661.6 [M+Na]+ calcd for C91H98O28
Octamer 8g: ESI-MS (m/z): 1896.7 [M+Na]+ calcd for C104H112O32
.
.