3080
J. T. Reeves et al. / Tetrahedron Letters 50 (2009) 3077–3080
168.1, 144.2, 135.7, 132.9, 127.4, 126.6, 125.7, 60.8. 58.5, 41.2,
26.8, 23.3, 13.8; Anal. Calcd for C17H24O4: C, 69.84; H, 8.27. Found:
C, 69.71; H, 8.40.
References and notes
1. (a) Smith, L. I.; Prichard, W. W. J. Am. Chem. Soc. 1940, 62, 771–777; (b) Nieman,
J. A.; Coleman, J. E.; Wallace, D. J.; Piers, E.; Lim, L. Y.; Roberge, M.; Andersen, R.
J. J. Nat. Prod. 2003, 66, 183–199.
2.4. General procedure for 1,1,3-trimethyl-3-arylindane forma-
tion. 5-Fluoro-3-(4-fluorophenyl)-1,1,3-trimethylindane (13)
2. For a 6-step regiospecific synthesis of 3,3,6-trimethylindan-1-one, see: Vogt, P.
F.; Molino, B. F.; Robichaud, A. J. Synth. Commun. 2001, 31, 679–684.
3. Holmberg, C. Liebiegs Ann. Chem. 1981, 4, 748–760.
4. Koo, J. J. Am. Chem. Soc. 1953, 75, 1891–1895.
A flask was charged with PPA (10.0 mL) and heated to 90 °C
with stirring. Compound 12 (1.0 g) was charged neat dropwise (so-
lid compounds were added portionwise). The reaction mixture was
held at 90 °C for the time listed in Table 1 (until consumption of
starting material as determined by HPLC analysis). The reaction
mixture was cooled to 30–40 °C, quenched with water (70 mL),
and stirred until all PPA was hydrolyzed. EtOAc was added and
the layers were separated. The organic phase was dried over
MgSO4, filtered, and concentrated to give the crude product, which
was purified by chromatography on silica gel (hexanes) to give 13
as a white solid, 345 mg, 75% yield. 1H NMR (400 MHz, CDCl3) d
7.15–7.08 (m, 3 H), 6.99–6.88 (m, 3 H), 6.78–6.73 (m, 1H), 2.38
(d, 1H, J = 12.8 Hz), 2.21 (d, 1H, J = 12.8 Hz), 1.65 (s, 3H), 1.32 (s,
3H), 1.03 (s, 3H); 13C NMR (100 MHz, CDCl3) d 163.5, 162.2,
161.1, 159.8, 150.8, 147.6, 146.0, 128.1, 128.0, 123.8, 123.7,
114.8, 114.6, 114.55, 114.3, 111.5, 111.3, 59.6, 50.2, 42.4, 30.8,
30.75, 30.5; Anal. Calcd for C18H18F2: C, 79.39; H, 6.66. Found: C,
79.20; H, 6.82.
5. Zimmerman, H. E.; Cassel, J. M. J. Org. Chem. 1989, 54, 3800–3816.
6. (a) Bergmann, E.; Taubadel, H.; Weiss, H. Chem. Ber. 1931, 64B, 1493–1501; (b)
Rosen, M. J. J. Org. Chem. 1953, 18, 1701–1705; (c) Petropoulos, J. C.; Fisher, J. J. J.
Am. Chem. Soc. 1958, 80, 1938–1941; (d) Higashimura, M.; Imamura, K.;
Yokogawa, Y.; Sakakibara, T. Chem. Lett. 2004, 33, 728–729.
7. (a) Mitsuhashi, T. J. Am. Chem. Soc. 1986, 108, 2394–2400; (b) Kondo, Y.;
Kusabayashi, S.; Mitsuhashi, T. J. Chem. Soc., Perkin Trans. 2 1988, 1799–1803;
(c) Hirota, H.; Mitsuhashi, T. Chem. Lett. 1990, 803–806.
8. For reactions involving oxidative addition of Pd or Ni to 2-vinyl-1,1-
di(alkoxycarbonyl)cyclopropanes see: (a) Shimizu, I.; Ohashi, Y.; Tsuji, J.
Tetrahedron Lett. 1985, 26, 3825–3828; (b) Yamamoto, K.; Ishida, T.; Tsuji, J.
Chem. Lett. 1987, 1157–1158; (c) Shimizu, I.; Aida, F. Chem. Lett. 1988, 601–604;
(d) Sumida, Y.; Yorimitsu, H.; Oshima, K. Org. Lett. 2008, 10, 4677–4679.
9. For examples of nucleophilic opening of 1,1-di(alkoxycarbonyl)cyclopropanes
see: (a) Blanchard, L. A.; Schneider, J. A. J. Org. Chem. 1986, 51, 1372–1374; (b)
Bambal, R.; Kemmitt, R. D. W. J. Chem. Soc., Chem. Commun. 1988, 11, 734–735;
(c) Ok, T.; Jeon, A.; Lee, J.; Lim, J. H.; Hong, C. S.; Lee, H.-S. J. Org. Chem. 2007, 72,
7390–7393.
10. For an example of an eliminative opening of
a
2,2-dimethyl-1,1-
di(alkoxycarbonyl)cyclopropane see: Krief, A.; Froidbise, A. Tetrahedron 2004,
60, 7637–7658.
11. For a retro-Michael addition of diethyl malonate from 1,5-diketone systems
see: Rao, H. S. P.; Jothilingam, S. J. Chem. Sci. 2005, 117, 27–32.
12. Cahiez, G.; Alami, M. Tetrahedron 1989, 45, 4163–5176.
13. Sun, H.-B.; Li, B.; Hua, R.; Yin, Y. Eur. J. Org. Chem. 2006, 4231–4236.
14. Colonge, J.; Pichat, L. Bull. Soc. Chim. Fr. 1949, 177–185.
15. Kelley, J. L.; Rigdon, G. K.; Cooper, B. R.; McLean, E. W.; Musso, D. L.; Orr, G. F.;
Selph, J. L.; Styles, V. L. U.S. Patent 6 124 284, 2000.
2.5. 1,1,3-Trimethyl-3-(naphthalen-1-yl)-2,3-dihydro-1H-
cyclopenta[a]naphthalene (21)
16. Takaki, K. S.; Watson, B. T.; Poindexter, G. S.; Epperson, J. R. U.S. Patent 5 661
186, 1997.
17. Peppe, C.; Lang, E. S.; Andrade, F. M.; Castro, L. B. Synlett 2004, 1723–1726.
18. Polovoi, Y. N.; Khudyakova, L. S. Zh. Prikl. Khim. 1969, 42, 1139–1144.
19. Morin, F. G.; Horton, W. J.; Grant, D. M.; Pugmire, R. J. J. Org. Chem. 1985, 50,
3380–3388.
20. Prout, F. S.; Huang, E. P. Y.; Hartman, R. J.; Korpics, C. J. J. Am. Chem. Soc. 1954,
76, 1911–1913.
21. Huang, X.; Chan, C. C.; Wu, Q. L. Tetrahedron Lett. 1982, 23, 75–76.
White solid; 1H NMR (400 MHz, CDCl3) d 7.92–7.45 (m, 8H),
7.26–7.05 (m, 3 H), 6.94–6.74 (m, 2H), 3.04 (d, 1H, J = 16 Hz),
2.01 (s, 3H), 2.00–1.90 (m, 1H), 1.61 (s, 3H), 1.50 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 146.6, 144.6, 143.7, 135.3, 134.3, 130.5,
129.2, 128.1, 127.5, 126.5, 126.1, 125.7, 124.9, 124.6, 124.5,
122.8, 59.3, 50.8, 44.1, 35.0, 34.6, 33.9; Anal. Calcd for C26H24: C,
92.81; H, 7.19. Found: C, 92.74; H, 7.29.