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Volumn 62, Issue 25, 1997, Pages 8750-8759

Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 2. Regioselective Lithiation of 2-Silylated-3-substituted Furan Rings

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EID: 0000484117     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971098b     Document Type: Article
Times cited : (27)

References (174)
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • For some recent examples, see: (a) Keay, B. A.; Dibble, P. W. Compr. Heterocycl. Chem. II 1996, 2, 395. (b) Fraga, B. M. Nat. Prod. Rep. 1992, 5, 217. (c) Faulkner, D. J. Nat. Prod. Rep. 1992, 9, 323. (d) Fraga, B. M. Nat. Prod. Rep. 1992, 9, 557. (e) Fraga, B. M. Nat. Prod. Rep. 1991, 8, 61. (f) Faulkner, D. J. Nat. Prod. Rep. 1991, 8, 269. (g) Fraga, B. M. Nat. Prod. Rep. 1990, 7, 515. (h) Faulkner, D. J. Nat. Prod. Rep. 1988, 5, 269. (i) Hanson, J. R. Nat. Prod. Rep. 1989, 5, 347. For the use of 3,4-disubstituted furans as intermediates in synthesis, see: (j) Froborg, J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1975, 40, 1595. (k) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (l) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. Chem. Lett. 1987, 2257. (m) Jung, M. E.; Usui, Y.; Vu, C. T. Tetrahedron Lett. 1987, 28, 5977. (n) Katagiri, N.; Akatsuka, H.; Haneda, T.; Kaneko, C. J. Org. Chem. 1988, 53, 5464. (o) Kanematsu, K.; Soejima, S.; Wang, G. Tetrahedron Lett. 1991, 32, 4761. (p) Eberbach, W.; Laber, N.; Bussenius, J.; Fritz, H.; Rihs, G. Chem. Ber. 1993, 126, 975.
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    • (f) We have recently used this chemistry for the synthesis of the furan portion of (+)-xestoquinone, see: Maddaford, S, P.; Andersen, N. G.; Cristofoli, W. A.; Keay, B. A. J. Am. Chem. Soc. 1996, 118, 10766. (g) Scott has used our methodology for the preparation of 2,3,4-trisubstituted furans, see: Danso-Danquah, R. E.; Scott, A. I. Tetrahedron 1993, 49, 8195.
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    • 13C NMR spectra, respectively. See: (a) Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of Organic Compounds, 5th ed.; John Wiley & Sons, Inc., 1991. (b) Biemann, K. (Translator from German). Tables of Spectral Data for Structure Determination of Organic Compounds; Boschke, F. L., Fresenius, W., Huber, J. F. K., Pungor, E., Rechnitz, G. A., Simon W., West, Th. S., Eds.; Springer-Verlag: Berlin, 1983.
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    • An alternative explanation is that the acidity of the C-4 hydrogen atom has increased relative to that of the C-5 hydrogen atom due to electronic factors resulting from the presence of a silicon atom at C-2 of the furan ring. Semiempirical calculations (PM3) on 2-(trimethylsilyl)-3-(hydroxymethyl)furan indicated that the electronic density at the furan carbon atoms and the C-4 and C-5 hydrogen atoms were not significantly changed relative to the electronic densities calculated for similar atoms in 3-(hydroxymethyl)furan; therefore we believe stereoelectronic factors are not the driving force for the observed C-4 lithiation.
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    • This explanation is akin to a "gearing" or "cogwheeling" phenomenon, which leads to a "conformational lock". For a discussion on "gearing", etc., see: Eliel, E.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; p 1160 and references therein.
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    • 4 dihedral angle ranging from +36° to +85°.
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    • We do not understand why compound 3 lithiates exclusively at C-4 in DME in the absence of an additive. The bidendate nature of this solvent may not be the reason since the lithiation of 3 in a THF-TMEDA mixture resulted in a C-4:C-5 mixture.
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    • See ref 2, p 68
    • See ref 2, p 68.
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    • We have shown that the γ anion can be trapped with a variety of electrophiles in good to excellent yields, see: Yu, S.; Beese, G.; Keay, B. A. J. Chem. Soc., Perkin Trans. 1 1992, 2729.
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    • 3 bonds were rotated independently by increments of 36° and a geometry optimization performed on the resulting intermediate structure. A total of 23 structures were obtained, and the Boltzman distribution was calculated at 298 K.


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