臺灣博碩士論文加值系統

詳見英文摘要

The thesis discusses several new tungsten and ruthenium mediated cycloaddition reactions and their application in organic synthesis. For convenience and better understanding, the thesis is divided in to three chapters. The first two chapters deals with tungsten mediated cycloaddition reactions and the third chapter deals with ruthenium mediated cycloaddition reactions and application in organic synthesis.
The synthesis of organic carbocyclic and heterocyclic systems from acyclic building blocks is typically achieved through the use of either condensation or cycloaddition process. The reactions of Co2(CO)8 with alkynes RCCR¢ form (RCCR¢)-Co2(CO)6 complexes. The versatility of these reactions is well recognized, and they are frequently employed as a key step in synthesis of complex molecules. Development of new synthetic method involving carbenoid intermediates has received considerable attention. Although there are numerous investigations on (RC≡CR¢)Co2(CO)6 complexes, generation of a carbenoid intermediate from this functionality remains entirely unknown. In chapter-I we describe several intramolecular cyclizations via carbenoid intermediates generated from Co2(CO)6 complexation of funtionalized alkynyltungsten compounds. The synthetic utility of these cyclizations is manifested in the synthesis of cyclopentenone derivatives.
The cycloaddition of alkynes and alkenes with organic substrate is widely used for the synthesis of carbocyclic and heterocyclic compounds. Epoxides and aziridines are important substances, and the cycloaddition of these molecules with alkenes alkynes is an interesting topic in organic synthesis. In chapter-II we report two useful cyclizations based on alkynyltungsten compounds, and each reaction involves sequential bond-breaking and —forming process. [3+2]-Cycloaddition of epoxides and aziridines with alkynes are hitherto unreported to the best of our knowledge. In this study, we describe a new cycloaddition of common epoxides and trans-aziridines with funtionalized alkynes. These methods are applicable to the enantiocontrolled synthesis of complex bicyclic lactones and lactams. Significant feature of this cycloaddition is that, it provides a one pot synthesis of bicyclic lactones via a tungsten enol ether.
In chapter-III we describe the syntheses of various chiral oxacyclic dienes via enyne metathesis using Grubbs Catalyst (PCy3)2Cl2Ru=CHPh. These oxacyclic dienes are designed to bear a (2S)-(alkoxy)ethyl group derived from natural (2S)-ethyl lactate. The role of this substituent is twofold in synthetic application (1) control of diastereoselective Diels-Alder reaction (2) easy degradation into a common functionality after cycloadditon reaction. Our present approach for the synthesis of chiral oxacyclic dienes was extended for the construction of enantiopure tricyclic furan derivatives.
Fused bicyclic [n.m.0] structural frameworks represent an important substructure in many natural products, and development of new synthetic approaches to these skeletons continues to be an important goal. Our enyne metathesis approach toward the synthesis of chiral oxacyclic dienes led us to focus on the construction of functionalized chiral oxabicyclic products that contain five-, six- and seven-membered rings by tandem RCM of dienynes using Grubbs ruthenium catalyst. Using this Tandem RCM approach variety of chiral fused bicyclic [n.m.0] rings can be constructed from simple precursors.

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENT iii
ABSTRACT v
LIST OF SCHEMES vii
LIST OF TABLES xii
LIST OF FIGURES xiii
LIST OF PUBLICATIONS xiv
ABBREVIATIONS xv
CHAPTER I: Intramolecular Cyclizations via Carbenoid Intermediates in Complexation of Alkynyltungsten Compounds with Co2(CO)8: A new Route to the Pauson-Khand Reaction.
Introduction 1
Results and Discussion 14
Conclusion 32
CHAPTER II: Tungsten-Promoted [3+2]-Cycloaddition of Epoxides and
Aziridines with Alkynes. A Facile Enantiospecific Synthesis of Bicyclic
Lactones.
Introduction 33
Results and Discussion 44
Conclusion 65
CHAPTER III: Synthesis of Chiral Oxacyclic Dienes via Ruthenium-Cataly-
-zed Enyne Metathesis: Useful Building Blocks for Chiral Tricyclic Oxy-
-gen Derivatives.
Introduction 66
Results and Discussion 75
Conclusion 86
Catalytic Ring Closing Metathesis of Dienynes: Construction of Fused Bicyclic
rings.
Introduction 87
Results and Discussion 90
Conclusion 97
EXPERIMENTAL SECTION 98
REFERENCES 184
CRYSTAL STRUCTURES, 1H AND 13C NMR SPECTRA 194
1H-1H AND 1H-13C COSY SPECTRA 320

References:
(1). Posner, G. H. Chem. Rev.1986, 86, 831.
(2). Schore, N. E Chem. Rev. 1988, 88, 1081.
(3). Dickson, R. S.; Fraser, P. J. Adv. Organomet. Chem. 1974, 12, 323.
(4). For synthetic applications of (RC≡CR)Co2(CO)6 complexes, see, review papers: (a) Caffyn, A. J. M.; Nicholas, K. M. In Comprehensive Organometallic Chemistry, Vol 12: Transition Metal Organometallics In Organic Synthesis; Abel, E. W., Stone, F. G. A., Wilkinson, G. Eds.; Pergamon Press: Oxford, 1995; Chapter 7, p 685. (b) Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic Molecules; University Science Books: Mill Valley, 1994; Chapter-8, 242.
(5). (a) Pauson, P. L. Tetrahedron 1985, 41, 5855. (b) Shore, N. E. In Comprehensive Organometallic Chemistry, Vol 12: Transition Metal Organometallics In Organic Synthesis; Abel, E. W.; Stone, F. G. A.; Wilkinson, G. Eds.; Pergamon Press: Oxford, 1995; Chapter 7.2, p 703. (c) Shore, N. E. In Comprehensive Organic Synthesis, Trost, B. M. Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1037.
(6). Recent papers for cobalt-mediated Pauson-Khand reactions (a) Fon-querna, S.; Moyano, A.; Pericas, M.; Riera, A. J. Am. Chem. Soc. 1997, 119, 10225. (b). Pagenkopf, B. L.; Livinghouse, T. M. J. Am. Chem. Soc. 1996, 118, 2285. (c) Krafft, M. E.; Wison, A. M.; Dasse, O. A.; Shao, B.; Cheung, Y. Y.; Fu, Z.; Bonaga, L.; Mollman, M. K. J. Am. Chem. Soc. 1996, 118, 6080. (d) Jeong, N. Hwang, S. H.; Lee, Y.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159. (e) Jordi, L. Ricart, S.; Vinas, J. M.; Moreto,. J. M. Organometallics 1997, 16, 2808.
(7). Review papers: (a) Nicholas, K. C. Acc. Chem. Res. 1987, 20, 207. (b) Nicolaou, K. C. Dai,. W. M. Angew. Chem., Int. Ed. Eng. 1991, 30, 1387.
(8). Najdi, S. D.; Olmstead, M. M.; Shore, N. E. J. Organomet. Chem. 1992, 431, 335.
(9). Application to synthesis of natural products, see examples: (a) Jamison, T. F. Shambayati, S.; Crowe, W. E.; Schreiber, S. L.; J. Am. Chem. Soc. 1997, 119. 4353. (b) Tormo, J.; Moyano, A.; Pericas, M. A.; Riera, A. J. Org. Chem. 1997, 62, 4851. (c) Magnus, P.; Becker, D. P. J. Am. Chem. Soc. 1987, 109, 7495.
(10). Khand, I. U.; knowx, G. R.; Pauson, P. L.; Watts, W. E.; Foremann, M. I.; J. Chem. Soc, Perkin Trans. I, 1973, 977.
(11). (a) Pauson, P. L.; Khand, I. U. Ann. N. Y. Acad. Sci. 1977, 295, 2-14. (b) Pauson, P. L. Tetrahedron, 1985, 41, 5855.
(12). (a) Schore, N. E. Chem. Rev. 1988, 88, 1081. (b) Schore, N. E. Organic Reactions 1991, 40, 1-90. (c) Schore N. E. In Comprehensive Organic Synthesis (Eds.: Trost, B. M.; Fleming I.), Pergamon Press, Oxford, 1991, Vol. 5, pp. 1037-1064. (d) Schore N. E. In Comprehensive Organometallic Chemistry II (Ed.: L. S. Hegedus), Pergamon Press, Oxford, 1995, Vol. 12, pp. 703-739.
(13). Schore, N. E.; Croudace M. C., J. Org. Chem. 1981, 46, 5436. (b) Exon, C.;
Magnus, P. J. Am. Chem. Soc. 1983, 105, 2477.
(14). (a) Exon, C.; Magnus, P. J. Am. Chem. Soc. 1983, 105, 2477. (b) Magnus P. and Principe, L. M. Tetrahedron Lett., 1985, 26, 4851.
(15). Roush, W. R.; Park, J. C. Tetrahedron Lett., 1991, 32, 6285.
(16). Moyano, A. Tetrahedron Lett., 1990, 31, 7505.
(17). Krafft, M. E.; Scott, I. L.; Romero, Feibelmann R. H. S.; Van Pelt, C. E. J. Am. Chem. Soc, 1993, 115, 7199.
(18). Billington D. C.; Willison, D. Tetrahedron Lett., 1984, 25, 4041.
(19). (a) Smit, W. A.; Kireev, S. L.; Nefedov O. M ; Tarasov, V. A. Tetrahedron Lett.,1989, 30, 4021; (b) Kim, D. (M. S). Dissertation, University of Minnesota at Duluth, 1988.
(20). (a) Knudsen M. J.; Schore, N. E. J. Org. Chem. 1984, 49, 5025; (b) Smit, V. A.; Gybin, A. S.; Veretenov S. O.; Shashkov, A. S Izv. Akad. Nauk SSSR, Ser. Khim., 1987, 232.
(21). (a) Veretenov, A. L.; Smit, W. A.; Vorontsova, L. G.; Kurella, M. G.; Caple, R.; Gybin, A. S. Tetrahedron Lett., 1991, 32, 2109, (b) Smit , A. J. Am. Chem. Soc., 1992, 114, 5555. (c) Schore N. E.; Knudsen, M. J. J. Org. Chem., 1987, 52, 569.
(22). (a) Thommer, M.; Gerber P.; Keese, R. Chimia, 1991, 45, 23, (b) Van der Waals, A.; Keese, R. J. Chem Soc., Chem. Commun., 1992, 570
(23). (a) Shambayati, S.; Crowe, W. E.; Schreiber, S. L. Tetrahedron Lett. 1990, 31, 5289. (b) Jeong, N.; Chung, Y. K.; Lee, B. Y.; Lee, S. H.; Yoo, S. E. Synlett 1991, 204. (c) Scmit, W. A.; Simonyan, S. O.; Tarasov, G. S.; Mikaelian, G. S.; Gybin, A. S.; Ibragimov. I. I.; Caple, R.; Froen, O.; Kraeger, A Synthesis 1989, 472. (d) Smit, W. A.; Gybin, A. S.; Shaskov, A. S.; Strychkov, Y. T.; Kyzmina, L. G.; Mikaelian, G. S.; Caple, R.; Swanson, E. D. Tetrahedron Lett. 1986, 27, 1241.
(24). Chung, Y. K.; Lee, B. Y.; Jeong, N.; Hudecek, M.; Pauson, P. L.; Organometallics. 1993, 12, 220.
(25). Pagenkopf, B. L.; Livinghouse,. T J. Am. Chem. Soc. 1996, 118, 2285.
(26). Sugihara, T. Yamada, M.; Ban, H.; Yamaguchi, M.; Kaneko, C.; Angew. Chem., Int., Ed. Engl. 1997, 36, 2801.
(27). Sugihara, T.; Yamada, M.; Yamaguchi, M.; Nishizawa, M. Synlett 1999, 771.
(28). Sugihara, T.; Yamaguchi, M. Synlett 1998, 1384
(29). Smit, W. A.; Gybin, A. S.; Shaskov, A. S.; Strychkov, Y. T.; Kyzmina, L. G.; Mikaelian, G. S.; Caple, R.; Swanson E. D. Tetrahedron Lett. 1986, 27, 1241.
(30). Krafft, M. E.; Romero, R. H.; Scott, I. L. J. Org. Chem. 1992, 57, 5277.
(31). Rautenstrauch, V.; Megard, P.; Conesa, J.; Kuster, W. Angew. Chem., Int. Ed. Engl. 1990, 29, 1413.
(32). Lee, B. Y.; Chung, Y. K.; Jeong, N.; Lee, Y.; Hwang, S. H. J. Am. Chem. Soc. 1994, 116, 8793.
(33). Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 4912.
(34). Jeong, N.; Hwang, S. H.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159.
(35). Jeong, N.; Lee, S. J.; Hwang, Y. S.; Chung, Y. K. to be published.
(36). a) Aumann, R.; Weidenhaupt, H. J. Chem. Ber. 1987, 120, 23. (b) Tamao, K.; Kobayashi, K.; Ito, Y. J. Am. Chem. Soc. 1988, 110, 1286. (c) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539.
(37). Jeong, N.; Lee, S. J.; Lee, B. Y.; Chung, Y. K. Tetrahedron Lett. 1993, 34, 4027.
(38). Hoye, T. R.; Suriano, J. A.; J. Am. Chem. Soc., 1993, 115, 1154.
(39). Negishi, E. I.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124.
(40). Grossman, R. B.; Buchwald, S. L. J. Org. Chem. 1992, 57, 5803.
(41). Dauben, W. G.; Kowalczyk, B. A. Tetrahedron Lett. 1990, 31, 635.
(42). Exon, C.; Magnus, P. J. Am. Chem. Soc. 1983, 105, 2477.
(43). Jamison, T. F.; Shambayati, S.; Crowe, W. E.; Schreiber, S. L J. Am. Chem. Soc. 1994, 116, 5505.
(44). Hua, D. H.; J. Am. Chem. Soc., 1986, 108, 3835; (b) Hua, D. H.; Coulter, M. J.; Badejo, I. Tetrahedron Lett., 1987, 28, 5465.
(45). (a) Mosses, R. A. Acc. Chem. Res. 1989, 22, 15. (b) Mosses, R. A. In Carbene; Jones, M., Jr., Moss, R. A. Eds.; Wiley: New York, 1973; pp 153. (c) Doyle, M. P.; Forbes, D. C. Chem Rev. 1998, 98, 911. (d) Doyle, M. P.; Mckervy, M. A.; Ye, T. In Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; Wiley: New York, 1997.
(46). (a) Li, W.-T., Lai, F.-C., Lee, G. H.; Peng, S. M.; Liu, R.-S. J. Am. Chem. Soc. 1998, 120, 4520. (b) Liang, K.-W. Liang, W.-T.; Li, G.-H.; Lee, S.-M.; Peng, R.-S.; Liu, J. Am. Chem. Soc. 1997, 119, 4404.
(47). Bruce, M. L.; Humphrey, M. G.; Mattisons, J. G.; Roy, S. K.; Swincer, A. G. Aust. J. Chem. 1984, 1041.
(48). (a) Beurich, H.; Vahrenkemp, H. Chem Ber. 1982, 115, 2385. (b) Beurich, H.; Blumhofer, R.; Vahrenkemp, H. Chem Ber. 1982, 115, 2385.
(49). Jeffery, J. C.; Lewis, D. B.; Lewis, G. E.; Parrott, M. J.; Stone, F. G. A. J. Chem. Soc., Dalton Trans. 1986, 1717.
(50). (a) Khand, I. U.; Pauson, P. L. J. Chem. Soc., Chem. Commun. 1974, 379. (b) Khand, I. U.; Pauson, P. L Heterocycles 1978, 11, 59.
(51). Pauson, P.L.; Khand, I. U. Ann. N.Y. Acad. Sci. 1977, 295,2.
(52). Shiu, Y.-T.; Madhushaw, R. J., Li, W.-T., Lin, Y.-C., Lee, G.-H., Peng, S.-M., Liao, F.-L., Wang, S.-L., Liu, R.-S. J. Am. Chem. Soc. 1999, 121, 4066.
(53). (a) Gothelf, K. V.; Jorgensen, K. A. Chem. Rev. 1998, 98, 863. (b) Tufariello,. J. J. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley & Sons: Chichester, 1984; Vol. 2, p 83. (c) Carruthers, W.; Cycloaddition in Organic Synthesis; Pergamon: Oxford, 1990. (d) Pindur, U.; Lutz, G.; Otto, C. Chem. Rev. 1993, 93, 741. (e) Togni, A.; Venanzi, L. M. Angew. Chem., Int. Ed. Engl. 1994, 33, 497.
(54). Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, J. R. Chem. Rev. 1996, 96, 635.
(55). Cycloadditions of aziridine with olefin and alkyne with cleavage of the C-C bond; see the following examples: (a) Sisko, J.; Weinreb, S. M. J. Org. Chem. 1991, 56, 3211. (b) Takano, S.; Iwabuchi, Y.; Ogasawara, K. J. Am. Chem. Soc. 1987, 109, 5523. (c) DeShong, P.; Kell, D. A.; Sidler, D. R. J. Org. Chem. 1985, 50, 2309. (d) Metra, P.; Hemelin, J. J. Chem. Soc., Chem. Commun. 1980, 1038. (e) Gaebert, C.; Siegner, C.; Mattay, J.; Toubartz, M.; Steenken, S. J. Chem. Soc., Perkin Trans. 2 1998, 2735. (f) Domingo, L. R. J. Org. Chem. 1999, 64, 3922.
(56). Cycloadditions of epoxide with olefin and alkyne with cleavage of the C-C bond; see the following examples: (a) Chou, W.-N.; White,. J. B.; Tetrahedron Lett. 1991, 32, 7637. (b) Gaebert, C.; Mattaay, J. Tetrahedron 1997, 53, 14297. (c) Palomino, E.; Schaap, A. P.; Heeg, M. J. Tetrahedron Lett. 1989, 30, 6801.
(57). Metra, P.; Hemelin,. J. J .Chem. Commun. 1980, 1038.
(58). Sisko, J.; Wienreb,. S. M. J. Org. Chem. 1991, 56, 3211.
(59). Masahiro, T.; Youichi, N.; Keiichiro, F. Heterocycles, 1994, 39, 39.
(60). Luigi, C.; Franco, B.; Piero. L. P. Synthesis, 1994, 287.
(61). Gaebbert, C.; Mattaay, J.; Tetrahedron, 1997, 53, 14297.
(62). Baeg, J.-O.; Alper, H. J. Am. Chem. Soc. 1994, 116, 1220.
(63). Cycloadditions of aziridine or epoxide with alkene with cleavage of the C-X bond; see: (a) Bergmeier, S. C.; Fundy, S. L.; Seth, P. P. Tetrahedron 1999, 55, 8025. (b) Schneider, M. R.; Mann, A.; Taddei, M. Tetrahedron Lett. 1996, 37, 8493. (c) M.; Nakagawa, M.; Kawahara, Org, Lett. 2000, 2, 953. (e) Sugita, Y.; Kimura, Y.; Yokoe, I. Tetrahedron Lett. 1999, 40, 5877.
(64). Schneider, M. R.; Mann, A.; Taddei, M. Tetrahedron Lett. 1996, 37, 8493.
(65). Bergmeier, S.C.; Fundy, S. L.; Seth, P. P. Tetrahedron Lett. 1999, 55, 8025.
(66). Sugita, Y.; Kimura, Y.; Yokoe, I. Tetrahedron Lett. 1999, 40, 5877.
(67). Marshall, J. A.; Dubay, W. J. J. Am. Chem. Soc. 1992, 114, 1450.
(68). Hidetomo, K.; Iwamoto, K.; Chatani, N.; Murahashi, S. J. Am. Chem. Soc. 1996, 118, 7634.
(69). Masako, N.; Michiaki, K. Org. Lett, 2000, 27, 953.
(70). Shim, J. G.; Yamamoto, Y. J. Org. Chem. 1996, 63, 3067.
(71). Bruce, M. I.; Chem. Rev., 1991, 91, 197.
(72). (a). Yamamoto H. In Comprehensive Organic Synthesis: Addition to C-X p bonds Part II, Trost B. M. and I. Fleming (Eds.), 1991, Vol. 2, Ch. 1.3, p.81, Pergamon, Oxford, (b) Fleming, I. In Comprehensive Organic Synthesis: Addition to C-X p bonds, Part I; Trost B. M. and Fleming I. (Eds.), 1991, Vol. 2, Ch. 2.2, p. 575, Pergamon Oxford, (c) Hosomi. A. Acc. Chem. Res. 1998, 21, 200; (d) Sukurai, H. Synlett 1989, 1.
(73). (a) Rosenblum. M. J. Organometal. Chem. 1986, 191, 300 (b) Rosenblum, M. Acc. Chem. Res. 1974, 7, 122, (c) Wojcicki, A. and Schuchart, C. E.; Chem. Rev. 1990, 105, 35, (d) Welker, M. E.; Chem. Rev. 1992, 92, 97 (d). Le, C.-L. and Liu, R.-S. Chem Rev. 2000, 100, 3127
(74). Till, C, P and Whiting, D. A. J. Chem. Commun. 1984, 590.
(75). Hanson, R. M.; Sharpless, K. B. J. Org. Chem. 1986, 51, 1922.
(76). Liang, K.-W.; Li, W.-T.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. J. Am. Chem. Soc. 1997, 119, 4404.
(77). Nicolaou, K. C.; Duggan, M. E.; Huang, C.-K.; Somers, P. K. J. Chem. Soc., Chem. Commun. 1985, 1359.
(78). Nicolaou, K. C.; Duggan, M. E.; Huang, C.-K.; Somers, P. K. J. Chem. Soc., Chem. Commun. 1985, 1359.
(79). Jeong, J. U.; Tao, B.; Sagasser, I.; Henniges, H.; Sharpless, K. B. J. Am. Chem. Soc. 1998, 120, 6844.
(80). Baldwin, J. E.; J. Chem. Soc. Chem. Commun. 1976, 734.
(81). (a) Boeckman, R. K.; Jr.; Breining, S. R.; Arvanitis, A. Tetrahedron 1997, 53, 8941. (b) Aelterman, W.; De kimpe, N. Tetrahedron 1998, 54, 2563. (c) Bigogno, C.; Danieli, B.; Lesma, G.; Passarella, D. Heterocycles, 1995, 41, 973. (d) Breitmaier, E.; B.; Potthoff, Chem. Ber. 1986, 119, 3204. (e) Breitmaier, E.; Ruffer, U. Synthesis 1986, 584.
(82). (a) Breitmaier, E.; Ruffer, U. Synthesis 1989, 623. (b) Cornwall, P.; Dell, C.P.; Knight, D. W. J. Chem. Soc. Perkin Trans. 1. 1993, 2395. (c) Chemler, S. R.; Iserloh, U.; Danishefsky, S. I. Org. Lett. 2001, 3, 2949.
(83). (a) Arrayas, R. G.; Liebeskind, L. S. J. Am. Chem. Soc. 2001, 123, 6185 (b) Li, W.-T.; Pan, M.-H.; Wu, Y.-R.; Wang, S.-L.; Liao, F.-L.; Liu, R.-S.; J. Org. Chem. 2000, 65, 3761. (c) Cheng, M.-H.; Yang, G.-M.; Chow, J.-F.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. J. Chem. Soc. Chem. Commun. 1992, 934.
(84). Pei, C.-C.; Liu, R.-S. Org. Lett, 2001, 3, 1295.
(85). Brosius, A. D.; Overmann, L. E.; Schwink, L. J. Am. Chem. Soc. 1999, 121, 700.
(86). Chemler, S. R.; Iserloh, U.; Danishefsky, S. J. Org. Lett. 2001, 3, 2949.
(87). For a review of enyne metathesis, see Mori, M. In Topics in Organometallic Chemistry, Fürstner, A.; Ed.; Springer-Verlag; Berlin Heidelberg, 1998; Vol. 1, p 133.
(88). (a) Mori, M.; Sakakibara, N.; Kinoshita, A. J. Org. Chem. 1998, 63, 6082. (b) Mori, M.; Kitamura, T.; Sakakibara, N.; Sato, Y. Org. Lett. 2000, 2, 543 (c) Mori, M.; Sakakibara, N.; Kinoshita, A. J. Am. Chem. Soc. 1997, 119, 12388. (d) Kinoshita, A.; Mori, M. J. Org. Chem. 1996, 61, 8356. (e) Mori, M.; Tonogaki, K.; Nishiguchi, N. J. Org. Chem. 2002, 67, 224. (f) Mori, M.; Kitamura, T.; Sato, Y. Synthesis. 2001, 654. (g) Kitamura, T.; Sato, Y.; Mori, M. Chem. Commun. 2001, 1258. (h). Trost, B. M.; Doherty, G. A. J. Am. Chem. Soc. 2000, 122, 3801. (i) Furstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305.
(89). (a) Duboc, R.; Henaut, C.; Savignac, M.; Genet, J.-P.; Bhatnagar, N. Tetrahedron Lett. 2001, 2461. (b) Clark, J. S.; Trevitt, G. P.; Boyall, D.; Stammen, B. J. Chem. Soc. Chem. Commun. 1998, 2629. (c) Clark, J. S.; Hamelin, O. Angew. Chem. 2000, 112, 380. (d) Stragies, R.; Voigtmann, U.; Blechert, S. Tetrahedron Lett. 2000, 41, 5465. (e). Hoye, T. R.; Donaldson, S. M.; Vos, T. Org. Lett. 1999, 1, 277.
(90). (a) Barrett, A. G. M.; Baugh, S. P. D.; Braddock, C.; Flack, K.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A.; White, A. J. P.; Williams, D. J. J. Org. Chem. 1998, 63, 7893. (b) Barrett, A. G. M.; Baugh, S. P. D.; Braddock, C.; Flack, K.; Gibson, V. C.; Procopiou, P. A. J. Chem. Soc. Chem. Commun. 1997, 1375. (c) Renaud, J.; Graf, C.-D.; Oberer,. L. Angew Chem.; Int. Ed. Engl. 2000, 39, 3101 (d) Schuster, M.; Lucas, N.; Blechert, S. Chem. Commun. 1997, 823. (e) Stragies, R.; Schuster, M.; Blechert, S. Angew Chem.; Int. Ed. Engl. 1997, 36, 2518. (f) Schürer, S. C.; Blechert, S. SynLett. 1998, 166. (g) Schuster, M. Blechert, S. Tetrahedron Lett. 1998, 39, 2295. (h) Stragies, R.; Schuster, M.; Blechert, S. Chem. Commun. 1999, 237. (i) Schürer, S. C.; Blechert, S. SynLett. 1999, 1879. (J) Schürer, S. C.; Blechert, S. Chem. Commun. 1999, 1203. (k) Schürer, S. C.; Blechert, S. Tetrahedron Lett. 1999, 40, 1877. (l) Kotha, S.; Halder, S.; Brahmachary, E.; Ganesh, T. SynLett. 2000, 853.
(91). (a) Appel, H. H.; Bond, R. P. M.; Overton, K. H. Tetrahedron. 1963, 19, 635. (b). Okuda, R. K.; Scheuer, J. J Org. Chem. 1983, 48, 1866. (c) Butler, M. S.; Capon, R. J. Aust. J. Chem. 1993, 46, 1255.
(92). Ley, S. V.; Armstrong, A.; Diez-Martin, D.; Ford, M. J.; Grice, P. J. Chem. Soc. Perkin, Trans. 1, 1991, 667.
(93). Hassner, A.; Alexanian, V. Tetrahedron. Lett. 1978, 49.
(94). Chen, M.-J.; Lo, C.-Y.; Chin, C.-C.; Liu, R.-S. J. Org. Chem. 2000, 65, 6362.
(95). (a) Wu, W.-L.; Yao, Z.-J.; Li, J.-C.; Xia, Y.; Wu, Y.-L. J. Org. Chem. 1995, 60, 3257. (b). Palomo, C.; Oiarbide, M.; Landa, A.; Esnal, A.; Linden, A. J. Org. Chem 2001, 66, 4180. (c) Inouye, M.; Fujimoto, K.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1999, 121, 1452.
(96). (a) Smulik, J. A.; Diver, S. T. Org. Lett. 2000, 2, 2271. (b) Smulik, J. A.; Diver, S. T. J. Org. Chem. 2000, 65, 1788. (c) Kinoshita, A.; Mori, M. Tetrahedron, 1999, 55, 8155.
(97). Matsutani, H.; Ichikawa, S.; Yaruva, J.; Kusumoto, T.; Hiyama, T. J. Am. Chem. Soc. 1997, 119, 4541.
(98). See, for instance: Natural Products Chemistry; Nakanishi, K. J. Ed.; Academic Press: New York, 1974; Vol 1-3.
(99).For recent reviews on ring-closure metathesis reactions see (a) Trnka, T.M.; Grubbs, R. H. Acc. Chem. Res,. 2001, 34, 18. (b) Furstner A.; Angew. Chem., Int. Ed. 2000, 39, 3012. (c) Armstrong, S. K. J. Chem.Soc., Perkin Trans-I. 1998, 54, 371. (d) Grubbs, R.H.; Chang, S. Tetrahedron. 1998, 54, 4413.
(100).For recent examples on the enynes RCM see: (a) Renaud, J.; Graf, C-D.; Observer, L. Angew. Chem., Int, Ed. 2000, 39, 3101. (b) Ackermann, L.; Bruneau. C.; Dixneuf, P.H. Synlett. 2001, 397. (c) Mori, M.; Kitamura, T.; Sato, Y. Synthesis. 2001, 654.
(101). For recent reviews see: (a) Maeir, M. E. Angew. Chem., Int. Ed. 2000, 39, 2073. (b) Yet, L. Chem. Rev. 2000, 100, 2963.
(102). (a) Kim, S.H.; Zuercher, J.; Bawden, N.B.; Grubbs, R.H. J. Org. Chem. 1996, 61, 1073.(b) Zuercher,W. J.; Scholl. M.; Grubbs, R. H. J.Org. Chem. 1998, 63, 4291.
(103). Previous reports on RCM: (a) Fu, G.C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 5426. (b) Fu, G.C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324. (c) Fu, G.C.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 3800. (d) Fu, G. C.; MGuyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9856. (e) Grubbs, R. H.; Miller, S. J.; Fu, G.C. Acc. Chem. Res. 1995, 28, 446. For recent applications of RCM to natural product. synthesis (f) Martin, S.F.; Liao, Y.; Rein, T. Tetrahedron Lett. 1994, 35, 691. (g) Borer, B.C.; Deerenberg, S.; Bieraugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191. For a review on Applications of Olefin Metathesis in Organic Synthesis; (h) Trost, B. M.; Ed.; Pergamon New York, 1991; Vol 5, Chapter 9.3.
(104). (a). Kim, S. H.; Bowden, N.; Grubbs, R. H. J. Am. Chem. Soc. 1994, 116, 10801. (b) Kim, S.H.; Zuercher, W. J.; Bowden, N.; Grubbs, R. H. J. Org. Chem. 1996, 61, 1073.
(105). Zuercher, W. J.; Scholl, M.; Grubbs, R. H. J. Org. Chem. 1998, 63, 4291.
(106) Codesido, E. M.; Castedo, L.; Granja, J. R. Org. Lett. 2001, 3, 1483.
(107). Boyer, F. D.; Hanna, I.; Ricard, L. Org. Lett. 2001, 3, 3095.
(108). Mukai, C.; Kasamatsu, E.; Ohyama, T.; Hanaoka, M. J. Chem. Soc., Perkin. Trans-I, 2000, 737.
(109). Corey E. J.; and Fuchs, P. L. Tetrahedron Lett., 1972, 13, 3769.
(110). Dub, M. Organometallic Compounds, 2nd ed.; Springer-Verlag: Berlin. 1966; Vol. 1.