Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene-Chromium Complexes: A Formal Total Synthesis of (±)-Vitamin D3

Journal of Organic Chemistry

Volumn 63, Issue 7, 1998, Pages 2325-2331

  Yan, Jingbo ^a   Herndon, James W ^b  

^a Bldg 142   (United States)

^b NEW MEXICO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001482246     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972186z     Document Type: Article

References (41)

1. (a) Herndon, J. W.; Matasi, J. J. J. Org. Chem. 1990, 55, 786-788.
2. (b) Herndon, J. W.; Matasi, J. J. Tetrahedron Lett. 1992, 33, 5725-5728
3. (a) Herndon, J. W.; Patel, P. P. Tetrahedron Lett. 1997, 38, 59-62.
4. (b) Herndon, J. W.; Turner, S. U. Tetrahedron Lett. 1989, 34, 295-296.
5. Watt, D. S.; McKenna, M. J.; Spencer, T. A. J. Org. Chem. 1967, 32, 2674-2678.
6. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
7. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
8. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
9. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
10. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
11. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
12. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
13. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
14. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
15. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
16. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
17. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
18. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
19. Construction via ring opening of norbornane derivatives: (a) Trost, B. M.; Bernstein, P. R.; Funfschilling, P. C. J. Am. Chem. Soc. 1979, 101, 4378-4380. (b) Grieco, P. A.; Takigawa, T.; Moore, D. R. J. Am. Chem. Soc. 1979, 101, 4380-4381. Stevens, R. V.; Lawrence, D. S. Tetrahedron 1985, 41, 93-100. Shimizu, I.; Matsuda, N.; Noguchi, Y.; Zako, Y.; Nagasawa, K. Tetrahedron Lett. 1990, 31, 4899-4902. Construction via stereoselective enolate alkylation: (e) Clase, J. A.; Money, T. Can. J. Chem. 1992, 70, 1537-1544. (f) Daniewski, A. R.; Warchol, T. Liebigs Ann. Chem. 1992, 965-973. Construction via stereoselective addition to exo-alkylidenecyclopentane derivatives: (g) Batchco, A. D.; Berger, D. E.; Davoust, S. G.; Wovkulich, P. M.; Uskoković, M. R. Helv. Chim. Acta 1981, 64, 1682-1687. (h) Hatekeyama, S.; Numata, H.; Takano, S. Tetrahedron Lett. 1984, 25, 3617-3620. Takahashi, T.; Yamada, H.; Tsuji, J. J. Am. Chem. Soc. 1981, 103, 5259-5261. Construction via stereoselective Michael addition: (j) Haynes, R. K.; Stokes, J. V.; Hambley, T. W. J. Chem. Soc., Chem. Commun. 1991, 58-60. (k) Grzymacz, P.; Marczak, S.; Wicha, J. J. Org. Chem. 1997, 62, 5293-5298. Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1469-1472. Construction via stereoselective hydrolysis-ring opening of an enamine-cyclobutene derivative: (m) Desmaele, D.; Ficini, J.; Guingant, A.; Touzin, A. M. Tetrahedron Lett. 1983, 24, 3083-3087. Construction via stereoselective Claisen rearrangement: (n) Chapleo, C. B.; Hallett, P.; Lythgoe, B.; Water-house, I.; Wright, P. W. J. Chem. Soc., Perkin Trans. 1 1977, 1211-1218.
20. For the latest synthesis, see: Pen, L.-R.; Tokoroyama, T. Tetrahedron Lett. 1992, 33, 1473-1474. See also ref 5f,h,m.
21. For a review of synthetic aspects of vitamin D, see: Zhu, G.-D.; Okamura, W. H. Chem. Rev. 1995, 95, 1877-1952.
22. 3, see ref 5m, followed by: (a) Kocienski, P. J.; Lythgoe, B.; Roberts, D. A. J. Chem. Soc., Perkin Trans. 1, 1980, 897-901. (b) Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2955-2959. Dawson, T. M.; Dixon, J.; Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2960-2966. Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1, 1980, 1400-1404. (e) Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1 1980, 1405-1406.
23. 3, see ref 5m, followed by: (a) Kocienski, P. J.; Lythgoe, B.; Roberts, D. A. J. Chem. Soc., Perkin Trans. 1, 1980, 897-901. (b) Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2955-2959. Dawson, T. M.; Dixon, J.; Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2960-2966. Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1, 1980, 1400-1404. (e) Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1 1980, 1405-1406.
24. 3, see ref 5m, followed by: (a) Kocienski, P. J.; Lythgoe, B.; Roberts, D. A. J. Chem. Soc., Perkin Trans. 1, 1980, 897-901. (b) Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2955-2959. Dawson, T. M.; Dixon, J.; Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2960-2966. Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1, 1980, 1400-1404. (e) Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1 1980, 1405-1406.
25. 3, see ref 5m, followed by: (a) Kocienski, P. J.; Lythgoe, B.; Roberts, D. A. J. Chem. Soc., Perkin Trans. 1, 1980, 897-901. (b) Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2955-2959. Dawson, T. M.; Dixon, J.; Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2960-2966. Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1, 1980, 1400-1404. (e) Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1 1980, 1405-1406.
26. 3, see ref 5m, followed by: (a) Kocienski, P. J.; Lythgoe, B.; Roberts, D. A. J. Chem. Soc., Perkin Trans. 1, 1980, 897-901. (b) Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2955-2959. Dawson, T. M.; Dixon, J.; Littlewood, P. S.; Lythgoe, B.; Saksena, A. K. J. Chem. Soc. C 1971, 2960-2966. Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1, 1980, 1400-1404. (e) Kocienski, P. J.; Lythgoe, B. J. Chem. Soc., Perkin Trans. 1 1980, 1405-1406.
27. For a review of the biological activity of vitamin D and its synthetic analogues, see: Bouillon, R.; Okamura, W. H.; Norman, A. W. Endocrine Rev. 1995, 16, 200-257.
28. (a) Wulff, W. D.; McCallum, J. S.; Kunng, F.-A. J. Am. Chem. Soc. 1988, 110, 7419-7434.
29. (b) Semmelhack, M. F.; Bozell, J. J.; Keller, L.; Sato, T.; Speise, E. J.; Wulff, W. D.; Zask, A. Tetrahedron 1985, 41, 5803-5812.
30. The first stereochemical label refers to the stereochemistry of heterocyclic ring substituents, and the second label refers to the stereochemistry of carbocyclic ring substituents.
31. Turner, S. U.; Herndon, J. W.; McMullen, L. A. J. Am. Chem. Soc. 1992, 114, 8394-8404.
32. 4-diene complexes have been proposed in the reaction of cyclopentadienones with group VI metal carbonyls. These results are more consistent with a simple reduction-protonation sequence, which employs an oxygen-bound complex. (a) Brown, D. A.; Hargaden, J. P.; McMullin, C. M.; Gogan, N.; Sloan, H. J. Chem. Soc. 1963, 4914-4918. (b) Adams, H.; Bailey, N. A.; Hempstead, P. D.; Morris, M. J.; Riley, S.; Beddoes, R. L.; Cook, E. S. J. Chem. Soc., Dalton Trans. 1993, 91-100.
33. 4-diene complexes have been proposed in the reaction of cyclopentadienones with group VI metal carbonyls. These results are more consistent with a simple reduction-protonation sequence, which employs an oxygen-bound complex. (a) Brown, D. A.; Hargaden, J. P.; McMullin, C. M.; Gogan, N.; Sloan, H. J. Chem. Soc. 1963, 4914-4918. (b) Adams, H.; Bailey, N. A.; Hempstead, P. D.; Morris, M. J.; Riley, S.; Beddoes, R. L.; Cook, E. S. J. Chem. Soc., Dalton Trans. 1993, 91-100.
34. Cyclopentadienones are excellent electron acceptors. (a) Östrich, S.; Broser, W.; Kurreck, H. Z. Naturforsch. B 1977, 32B, 686-692. (b) Burk, M. J.; Calabrese, J. C.; Davidson, F.; Harlow, R. L.; Roe, D. C. J. Am. Chem. Sac. 1991, 113, 2209-2222.
35. Cyclopentadienones are excellent electron acceptors. (a) Östrich, S.; Broser, W.; Kurreck, H. Z. Naturforsch. B 1977, 32B, 686-692. (b) Burk, M. J.; Calabrese, J. C.; Davidson, F.; Harlow, R. L.; Roe, D. C. J. Am. Chem. Sac. 1991, 113, 2209-2222.
36. This process is anticipated to be very rapid at the reaction temperature. For a recent example, see: Himeda, Y.; Yamataka, H.; Ueda, I.; Hatanaka, M. J. Org. Chem. 1997, 62, 6529-6538.
37. (a) Caine, D. Org. React. 1976, 23, 1-258.
38. (b) House, H. O.; Giese, R. W.; Kronberger, K.; Kaplan, J. P.; Simeone, J. F. J. Am. Chem. Soc. 1970, 92, 2800-2810.
39. Herndon, J. W.; Turner, S. U.; McMullen, L. A.; Matasi, J. J.; Schnatter, W. F. K. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1994; Vol. III, pp 51-95.
40. See the Supporting Information.
41. Desmaele, D.; Ficini, J.; Guingant, A.; Kahn, P. Tetrahedron Lett. 1983, 24, 3079-3082.