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R. Zimmer et al.
LETTER
(7) (a) Flögel, O.; Dash, J.; Brüdgam, I.; Hartl, H.; Reissig,
thank Prof. A. P. Marchand for the donation of a fair amount of di-
ketone 1.
H.-U. Chem. Eur. J. 2004, 10, 4283. (b) Dash, J.; Lechel,
T.; Reissig, H.-U. Org. Lett. 2007, 9, 5541. (c) Lechel, T.;
Dash, J.; Brüdgam, I.; Reissig, H.-U. Eur. J. Org. Chem.
2008, 3647.
References and Notes
(8) (a) Gwiazda, M.; Reissig, H.-U. Synlett 2006, 1683.
(b) Gwiazda, M.; Reissig, H.-U. Synthesis 2008, 990.
(9) Kaden, S.; Reissig, H.-U.; Brüdgam, I.; Hartl, H. Synthesis
2006, 1351.
(10) Sörgel, S.; Azap, C.; Reissig, H.-U. Org. Lett. 2006, 8, 4875.
(11) (a) Reissig, H.-U.; Hormuth, S.; Schade, W.; Okala
Amombo, M.; Watanabe, T.; Pulz, R.; Hausherr, A.;
Zimmer, R. J. Heterocycl. Chem. 2000, 37, 597.
(b) Brasholz, M.; Reissig, H.-U.; Zimmer, R. Acc. Chem.
Res. 2008, in press.
(12) Watanabe, T.; Reissig, H.-U., unpublished results.
(13) (a) Jeong, I.-Y.; Nagao, Y. Synlett 1999, 579. (b) Voigt, B.;
Brands, M.; Goddard, R.; Wartchow, R.; Butenschön, H.
Eur. J. Org. Chem. 1998, 2719.
(14) Reviews: (a) Marchand, A. P. Synlett 1991, 73.
(b) Marchand, A. P. Aldrichimica Acta 1995, 28, 95.
(15) Marchand, A. P.; Chong, H.-S.; Ganguly, B. Tetrahedron:
Asymmetry 1999, 10, 4695.
(1) Reviews: (a) Zimmer, R. Synthesis 1993, 165. (b) Zimmer,
R.; Khan, F. A. J. Prakt. Chem. 1996, 338, 92. (c) Zimmer,
R.; Dinesh, C. U.; Nandanan, E.; Khan, F. A. Chem. Rev.
2000, 100, 3067. (d) Tius, M. A. Acc. Chem. Res. 2003, 36,
281. (e) Zimmer, R.; Reissig, H.-U. Donor-Substituted
Allenes, In Modern Allene Chemistry; Krause, N.; Hashmi,
A. S. K., Eds.; Wiley-VCH: Weinheim, 2004, 425. (f) Tius,
M. A. Cyclizations of Allenes, In Modern Allene Chemistry;
Krause, N.; Hashmi, A. S. K., Eds.; Wiley-VCH: Weinheim,
2004, 817. (g) Tius, M. A. Eur. J. Org. Chem. 2005, 2193.
(h) Reissig, H.-U.; Zimmer, R. In Science of Synthesis, Vol.
44; Krause, N., Ed.; Thieme: Stuttgart, 2007, 301. (i) Tius,
M. A. 1-Methoxyallenyl Lithium, In Encyclopedia of
Reagents for Organic Synthesis, Vol. 5; Paquette, L. A., Ed.;
Wiley: Chichester, 1995, 3316. (j) Zimmer, R.; Reissig,
H.-U. 1-Methoxyallenyl Lithium, In Encyclopedia of
Reagents for Organic Synthesis, 1st update; Paquette, L. A.,
Ed.; Wiley: Chichester, 2005.
(16) Govender, T.; Hariprakasha, H. K.; Kruger, H. G.;
Marchand, A. P. Tetrahedron: Asymmetry 2003, 14, 1553.
(17) (a) Marchand, A. P.; Alihodžić, S.; McKim, A. S.; Kumar,
K. A.; Mlinarić-Majerski, K.; Šumanovac, T.; Bott, S. G.
Tetrahedron Lett. 1998, 39, 1861. (b) Marchand, A. P.;
Hazlewood, A.; Huang, Z.; Vadlakonda, S. K.; Rocha, J.-D.
R.; Power, T. D.; Mlinarić-Majerski, K.; Klaic, L.; Kragol,
G.; Byran, J. C. Struct. Chem. 2003, 14, 279. (c) Marchand,
A. P.; Gore, V. K.; Srinivas, G. Heterocycles 2003, 61, 541.
(d) Romański, J.; Marchand, A. P. Polish J. Chem. 2004, 78,
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(2) (a) Zimmer, R.; Reissig, H.-U. Angew. Chem. Int. Ed. Engl.
1988, 27, 1518; Angew. Chem. 1988, 100, 1576.
(b) Zimmer, R.; Reissig, H.-U. Liebigs Ann. Chem. 1991,
553. (c) Zimmer, R.; Angermann, J.; Hain, U.; Hiller, F.;
Reissig, H.-U. Synthesis 1997, 1467. (d) Zimmer, R.;
Orschel, B.; Scherer, S.; Reissig, H.-U. Synthesis 2002,
1553. (e) Zimmer, R.; Collas, M.; Czerwonka, R.; Hain, U.;
Reissig, H.-U. Synthesis 2008, 237.
(3) (a) Schade, W.; Reissig, H.-U. Synlett 1999, 632. (b) Pulz,
R.; Cicchi, S.; Brandi, A.; Reissig, H.-U. Eur. J. Org. Chem.
2003, 1153. (c) Helms, M.; Schade, W.; Pulz, R.; Watanabe,
T.; Al-Harrasi, A.; Fisera, L.; Hlobilova, I.; Zahn, G.;
Reissig, H.-U. Eur. J. Org. Chem. 2005, 1003.
(4) (a) Hoff, S.; Brandsma, L.; Arens, J. F. Recl. Trav. Chim.
Pays-Bas 1969, 88, 609. (b) Gange, D.; Magnus, P. J. Am.
Chem. Soc. 1978, 100, 7746. (c) Gange, D.; Magnus, P.;
Bass, L.; Arnold, E. V.; Clardy, J. J. Am. Chem. Soc. 1980,
102, 2134. (d) Magnus, P.; Albaugh-Robertson, P. J. Chem.
Soc., Chem. Commun. 1984, 804. (e) Hormuth, S.; Reissig,
H.-U. J. Org. Chem. 1994, 59, 67. (f) Hormuth, S.; Schade,
W.; Reissig, H.-U. Liebigs Ann. 1996, 2001. (g) Flögel, O.;
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(18) Cookson, R. C.; Crundwell, E.; Hill, R. R.; Hudec, J.
J. Chem. Soc. 1964, 3062.
(19) Bisallenyl Adduct 4
Methoxyallene (4.20 g, 60.0 mmol) was dissolved in dry
THF (35 mL) and treated with n-BuLi (16.0 mL, 40.0 mmol,
2.5 M in hexanes) at –40 °C under argon atmosphere. After
5 min the solution of 2 was cooled to –78 °C and diketone 1
(0.522 g, 3.00 mmol, dissolved in 5 mL of THF) was added
within 5 min. The reaction mixture was stirred for 2 h at
–78 °C and quenched with sat. aq NH4Cl solution (25 mL).
Warmup to r.t. was followed by extraction with Et2O (3 × 30
mL) and drying (Na2SO4). Purification of the crude product
by recrystallization (hexane–Et2O) provided 4 (0.678 g,
74%) as a beige-colored solid, mp 148–150 °C. 1H NMR
(250 MHz, CDCl3): d = 1.03, 1.54 (AB system, JAB = 10.5
Hz, 2 H, CH2), 2.25–2.46, 2.61–2.73 (2 m, 4 H each, 8 CH),
3.43 (s, 6 H, OMe), 5.46 (s, 2 H, OH), 5.48 (s, 4 H, =CH2).
13C NMR (62.9 MHz, CDCl3): d = 196.6 (s, C=C=CH2),
137.5 (s, =C=COMe), 91.8 (t, =C=CH2), 79.1 (s, C-3, C-5),
56.6 (q, OMe), 47.8, 44.8, 40.7, 33.8 (4 d, CH), 41.4 (t, CH2).
IR (KBr): 3630–3150 (OH), 3020–2820 (=CH, CH), 1930
(C=C=C), 1650 (C=C) cm–1. MS (EI, 80 eV): m/z (%) = 314
(6) [M]+, 281 (44), 161 (46), 147 (66), 115 (70), 103 (34), 69
(65), 55 (100), 43 (38). HRMS (80 eV): m/z calcd for
C19H22O4: 314.1518; found: 314.1543. Anal. Calcd for
C19H22O4 (314.4): C, 72.59; H, 7.05. Found: C, 71.81; H,
6.97.
(h) Hölemann, A.; Reissig, H.-U. Synthesis 2004, 1963.
(i) Brasholz, M.; Reissig, H.-U. Synlett 2007, 1294.
(j) Brasholz, M.; Reissig, H.-U. Angew. Chem. Int. Ed. 2007,
46, 1634; Angew. Chem. 2007, 119, 1659.
(5) (a) Breuil-Desvergnes, V.; Compain, P.; Vatèle, J.-M.; Goré,
J. Tetrahedron Lett. 1999, 40, 5009. (b) Breuil-Desvergnes,
V.; Compain, P.; Vatèle, J.-M.; Goré, J. Tetrahedron Lett.
1999, 40, 8789. (c) Okala Amombo, M.; Hausherr, A.;
Reissig, H.-U. Synlett 1999, 1871. (d) Breuil-Desvergnes,
V.; Goré, J. Tetrahedron 2001, 57, 1939. (e) Breuil-
Desvergnes, V.; Goré, J. Tetrahedron 2001, 57, 1951.
(f) Flögel, O.; Okala Amombo, M. G.; Reissig, H.-U.; Zahn,
G.; Brüdgam, I.; Hartl, H. Chem. Eur. J. 2003, 9, 1405.
(g) Flögel, O.; Reissig, H.-U. Synlett 2004, 895.
(h) Chowdhury, M. A.; Reissig, H.-U. Synlett 2006, 2383.
(i) Kaden, S.; Reissig, H.-U. Org. Lett. 2006, 8, 4763.
(6) Kaden, S.; Brockmann, M.; Reissig, H.-U. Helv. Chim. Acta
2005, 88, 1826.
(20) Compound 5
To a solution of 4 (0.205 g, 0.655 mmol) in CH2Cl2 (13 mL)
mesyl chloride (0.082 g, 0.723 mmol, dissolved in 2 mL of
CH2Cl2) and Et3N (0.658 g, 6.55 mmol) were added at 0 °C.
The solution was warmed up to r.t. and stirred for additional
Synlett 2008, No. 13, 2046–2050 © Thieme Stuttgart · New York