油菜甾醇内酯及其类似物侧链部分的立体选择性合成及过渡金属催化反应研究及在合成中的应用
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摘要
本论文主要以油菜甾醇内酯及其类似物的侧链部分的合成新方法，(4R，5S)-O-Acetyl-Osmundalactone的不对称全合成，铂催化反应研究，共分为三部分：
一．构筑油菜甾醇内酯及其类似物的侧链部分
1．以手性甾体醛为原料，以手性醛诱导的不对称Aldol反应、羰基α位差向异构化反应以及底物控制的不对称氢化为关键步骤构筑C_(-22)／C_(-23)／C_(-24)连续的3个不对称中心或C_(-22)／C_(-24)2个手性中心，成功构筑了油菜甾体化合物的侧链部分，为这几类化合物的合成提供了一条简单易行、方便便宜、收率高、立体选择性好的路线。
2．实验发现，强碱性条件下；α-硅氧酮在α位发生Aldol反应时，保护基TBS，TBDPS等会发生1，4-氧氧硅迁移现象。
二．(4R，5S)-O-Acetyl-Osmundalactone的不对称全合成
以L-乳酸乙酯为原料，以利用Sharpless环氧化反应和2，3-环氧醇的碘代重排反应构筑C_(-4)的不对称中心，通过RCM反应构筑六元内脂环，完成了此化合物的不对称全合成工作。
三．Pt催化的反应研究
PtCl_2催化的1，6-烯炔环异构化伴随炔丙基酯重排反应。一般情况，炔丙基酯在PtCl_2的催化下发生1，3-酯重排得到金属联烯，发生Diels-Alder-type反应。1，3-酯重排是关键步骤。
This thesis mainly aims at the studies on novel construction of the side chains ofbrassinolide and related compounds, and the asymmetric total synthesis of(4R,5S)-O-Acetyl-Osmundalactone, and studies on the platinum catalyzed reaction.It mainly consists of the following three parts:
PartⅠ: Novel construction of the brassinolide and related compounds' sidechains.
1. We report here a new method for constructing the side chains of brassinolide fromsteroidal-aldehyde, which is stereoselective and produces high yields. The key stepsof this routes included a highly stereoselective asymmetry aldol reaction induced bythe chiral aldehyde, the epimerization of a position of carbonyl and asymmetryhydrogenation induced by the chiral intermediate.
2. Novel phenomenon that the silyl groups migrated fromα-oxygen toβ-oxygen inlithium and sodium aldol reaction ofαposition ofα-silyloxy ketone was observed forthe first time in this paper.
PartⅡ: The asymmetric total synthesis of (4R,5S)-O-Acetyl-Osmundalactone.
Efficient asymmetric total synthesis of (4R,5S)-O-Acetyl-Osmundalactone has beencarried out in several steps from L-ethyl lactate. The key steps included Sharplessasymmetric epoxidation and RCM reaction.
PartⅢ: The platinum catalyzed reaction.
A platinum catalyzed cycloisomerization of 1,6-enyne coupling with therearrangement chemistry of propargylic ester has been developed. Most probably,under platinum catalysis, propargylic ester undergoes the 1,3-acyloxy migration to afford metal allene intermediate, which is followed by the Diels-Alder type reaction.1,3-Acyloxy migration is the key step during the transformation.
一．构筑油菜甾醇内酯及其类似物的侧链部分
1．以手性甾体醛为原料，以手性醛诱导的不对称Aldol反应、羰基α位差向异构化反应以及底物控制的不对称氢化为关键步骤构筑C_(-22)／C_(-23)／C_(-24)连续的3个不对称中心或C_(-22)／C_(-24)2个手性中心，成功构筑了油菜甾体化合物的侧链部分，为这几类化合物的合成提供了一条简单易行、方便便宜、收率高、立体选择性好的路线。
2．实验发现，强碱性条件下；α-硅氧酮在α位发生Aldol反应时，保护基TBS，TBDPS等会发生1，4-氧氧硅迁移现象。
二．(4R，5S)-O-Acetyl-Osmundalactone的不对称全合成
以L-乳酸乙酯为原料，以利用Sharpless环氧化反应和2，3-环氧醇的碘代重排反应构筑C_(-4)的不对称中心，通过RCM反应构筑六元内脂环，完成了此化合物的不对称全合成工作。
三．Pt催化的反应研究
PtCl_2催化的1，6-烯炔环异构化伴随炔丙基酯重排反应。一般情况，炔丙基酯在PtCl_2的催化下发生1，3-酯重排得到金属联烯，发生Diels-Alder-type反应。1，3-酯重排是关键步骤。
This thesis mainly aims at the studies on novel construction of the side chains ofbrassinolide and related compounds, and the asymmetric total synthesis of(4R,5S)-O-Acetyl-Osmundalactone, and studies on the platinum catalyzed reaction.It mainly consists of the following three parts:
PartⅠ: Novel construction of the brassinolide and related compounds' sidechains.
1. We report here a new method for constructing the side chains of brassinolide fromsteroidal-aldehyde, which is stereoselective and produces high yields. The key stepsof this routes included a highly stereoselective asymmetry aldol reaction induced bythe chiral aldehyde, the epimerization of a position of carbonyl and asymmetryhydrogenation induced by the chiral intermediate.
2. Novel phenomenon that the silyl groups migrated fromα-oxygen toβ-oxygen inlithium and sodium aldol reaction ofαposition ofα-silyloxy ketone was observed forthe first time in this paper.
PartⅡ: The asymmetric total synthesis of (4R,5S)-O-Acetyl-Osmundalactone.
Efficient asymmetric total synthesis of (4R,5S)-O-Acetyl-Osmundalactone has beencarried out in several steps from L-ethyl lactate. The key steps included Sharplessasymmetric epoxidation and RCM reaction.
PartⅢ: The platinum catalyzed reaction.
A platinum catalyzed cycloisomerization of 1,6-enyne coupling with therearrangement chemistry of propargylic ester has been developed. Most probably,under platinum catalysis, propargylic ester undergoes the 1,3-acyloxy migration to afford metal allene intermediate, which is followed by the Diels-Alder type reaction.1,3-Acyloxy migration is the key step during the transformation.
引文
1．唐除痴，李煜昶，陈彬，杨华铮，金桂玉．农药化学[M]．南开大学出版社，天津，1998，p．4．
2. Buchel, K. H. Chemistry of Pesticides, John Willey &Sons, New York, 1983, p. 6.
3．樊德方，黄幸舒，农药的污染与防治，科学出版社，北京，1982，p．2．
4．相关综述，参考文献[1]，p．597。
5. Michell, J. W.; Mandava, N.; Worley, J. F.; Plimmer, J. R.; Smith, M. V. Nature, 1970, 225, 1065;
6. Grove, M. D.; Spence, G. F.; Rohwedder, W. K.; Mandava, N.; Worley, J. F.; Warthen, J. D. Jr.; Stefrens, G. L.; Flippen-Anderson, J. L.; Cook, J. C. Jr. Nature, 1979, 281,216;
7. Yokota, T. Tetrahedron Lett., 1982, 23, 1275.
8. Maeda, E. Physiol. Plant., 1965, 18, 813;
9. Ikeda, M. Agrio. Biol. Chem., 1983, 42, 655;
10. Baba, T. Agrio. Biol. Chem., 1983, 47, 659;
11. Yokota, T.; Baba, T. Agrio. Biol. Chem., 1983, 47, 1409;
12. Takatsuto, S. "25th Symposium on the Chemistry of Natural Products, Tokyo ", 1982, 290;
13. Takatsuto, S. J.. Chromatogr, 1982, 233;
14. Abe, H. Agrio. Biol. Chem.,1984, 48, 2171.
15. Schneide, J. A. Tetrahedron Lett., 1983, 24, 3859.
16. Khripach, V. A.; Zhabinskii, V. N.; de Groot, A. E. Brassinosteroids, A New Class of Plant Hormones. Academic Press, 1999, p19.
17. Abe, H.; in Brassinosteroids; Chemistry, Bioactivity, and Appllications, ed. Cutler, H. G.; Yokota, T.; Adam, G.; American Chemical Society, Washington, 1991, p. 200.;
18. Abe, H.; Nakamura, K.; Morishita, T.; Uchiyama, M.; Takatsuto, S.; Ikekawa, N. Agric. Biol. Chem., 1984, 48, 1103;
19. Abe, H.; Takatsuro, S.; Nakayama, M.; Yokota, T.; Biosci. Biotechnol. Biochem., 1995, 59, 176;
20. Schmidt, J.; Schmidt, J.; Spengler, B.; Yokota, Y.; Nakayama, M.; Takatsuto, S.; Voigt, B.; Adam, G. Phytochemistry, 1995, 38, 1095;
21. Yakota, T.; Nakayama, M.; Wakisaka, T.; Schmidt, J.; Adam, G. Biosci. Biotechnol. Biochem., 1994, 58, 1183;
22. Suzuki, Y.; Yamaguchi, I.; Yokota, T.; Takahashi, N. Agric. Biol. Chem., 1986, 50, 3133;
23. Gamoh, K.; Okamoto, N.; Takatsuto, S.; Tcjima, I. Anal, Chim. Atca, 1990, 228, 101;
24. Abe, H.; Honjo, C.; Kyokawa, Y.; Asakawa, S.; Natsume, M.; Narushima, M. Biosci. Biotechnol. Biochem., 1994, 58, 986;
25. Asakawa, S.; Abe, H.;Kyokawa, Y.; Nakamura, S.; Natsume, M. Biosci. Biotechnol. Biochem., 1994, 58, 219;
26. Ikeda, M.; Takatsuto, S.; Sassa, T.; Ikekawa, N.; Nukima, M. Agric. Biol. Chem., 1983, 47, 655;
27. Arima, M.; Yokota, T.; Takahashi, N. Phytochemistry, 1984, 23, 1587.
28. Abe, H.; Morishita, T.; Marumo, S.; Munakata, K.; Takatsuto, S.; Idikawa, N. Agric. Biol. Chem. 1982, 46, 2609.
29. Abe, H.; Morishita, T.; Uchiyama, M.; Takatsuto, S.; Ikekawa, N.; Ikeda, M.; Sassa, T.; Kitsuwa, T.; Marumo, S. Experientia, 1983, 39, 351.
30. Yokota, T.; Morita, M.; Takahashi, N. Agric. Biol. Chem., 1995, 40, 907.
31. Yokota, T.; Koba, S.; Kim, S.-K.; Tskatsuto, S.; Ikekawa, N.; Sakakioara, M.; Okada, K.; M. K.; Takahashi, N. Agric. Biol. Chem., 1987, 51, 1625.
32. Yokota, T.; Kim, S.-K.; Ko, Y.; Ogino, Y.; Takahashi, N.; in Conjugated plant hormones, structure metabolism and function, eds. Schreiber, K.; Sutte, H. R.; Sembdner, G. VEG Deuchter Verlag der wissenschtten, 1987, p-288.
33. Kim, S.-K.; Yokota, T.; Takahashi, N. Agric. Biol. Chem., 1987, 51, 2303.
34. Kim, S.-K.; in Brassinosteroids Chemistry, Bioactivity, and Applications, cd. Cutler, H. G.; Yokota, T.; Adam, G.; American Chemical Society, Washington, 1991, p.26.
35. Ikekawa, N.; Takatsuto, S.; Kitsuwa, T.; Saito, H.; Morishita, T.; Abe, H. J. Chromatogr., 1984, 290, 289.
36. Morishita, T.; Abe, H.; Uchiyama, M.; Marumo, S.; Takatsuto, S.; Ikekawa, N.; Phytochemistry, 1983, 22, 1051.
37. Abe, H.; Morishita, T.; chiyama, M.; Takatsuto, S.; Ikekawa, N.; Agric. Biol. Chem., 1994, 48, 2171.
38. Suzuki, Y.; Yamaguchi, I.; Takahashi, N. Agric. Biol. Chem., 1985, 49, 49.
39. Yokota, T.; Arima, M.; Tal mashi, N.; Takatsuto, B.; Ikekawa, N.; Takematsu, T. Agric. Biol. Chem., 1983, 47, 2419.
40. Yokota, T.; Kim, S.-K.; Fuk, Y.; Takahashi, N.; Takeuchi, Y.; Takematsu, T. Phytochemistry, 1987, 25, 503.
41. Takatsuto, S. Tetrahedron Lett., 1983, 24, 1173.
42. Mori, K. Agric. Biol. Chem., 1983, 47, 97.
43. Sakakibara, M.; Mori, K.; Agric. Biol. Chem., 1983, 47, 336.
44. For reviews, see: (a) Back, T. G.; Baron, D. L.; Lou, W.; Nakajima, S. K. J. Org. Chem., 1997, 62, 1179-1182;
(b) Back, T. G.; Krishna, M. V. Can. J. Chem., 1993, 71, 156-163;
(c) Back, T. G.; Janzen, L.; Nakajima, S. K.; Pharis, R. P. J. Org. Chem., 1999, 64, 5494-5498;
(d) Back, T. G.; Janzen, L.; Nakajima, S. K.; Pharis, R. P. J. Org. Chem. 2000, 65, 3047-3052;
(e) Baron, D. L.; Luo, W.; Janzen, L.; Pharis, R. P.; Back, T. G. Phytochemistry, 1998, 49, 1849-1858;
(f) Fujioks, S.; Noguchi, T.; Takatsuto, S.; Yoshida, S. Phytochemistry, 1998, 49, 1841-1848;
(g) Fujioks, S.; Noguchi, T.; Watanabe, T.; Takatsuto, S.; Yoshida, S. Phytoche mistry, 2000, 53, 549-552;
(h) Fujioks, S.; Sakurai, A.; Natural Product Reports, 1997, 14, 1-10;
(i) Sung, G. C. Y.;; Janzen, L.; Pharis, R. P.; Back, T. G. Phytochemistry, 2000, 55, 121-126.
45. Mori, K,; Takeuchi, T. Liebigs Ann. Chem., 1988, 815.
46. (a) Honda, T.; Keino, K.; Tsubuki, M. J. Chem. Soc., Chem. Commun., 1990, 650;
(b) Tsubuki, M.; Keino, K.; Honda, T. J. Chem. Soc.,Perkin Trans 1,, 1992,2643.
47. Takatsuto, S.; Yazaka, N.; Ikekawa, N. Phytochemistry, 1984, 23, 525.
48. Zhou, W. S.; Huang, L. F.; Sun, L. Q.; Pan, X. F. J. Chem. Soc., Perkin Trans 1, 1986, 108, 7055.
49. Hayashi, S.; Hohjoh, T.; Shida, A.; Ikekawa, N. Eur Pat. Appl. EP, 282 984(CA: 110, 95 639s).
50. Huang, L. F.; Zhou, W. S. J. Chem. Soc., Perkin Trans 1, 1994, 3579.
51. (a) Li, W. D. Z.; Li, Y.; Li, Y. L. Tetrahedron Lett., 1999, 40, 966;
(b) Li, Y. L.; Li, W. D.; Li, Y. J. Chem. Soc. Perkin Trans I, 1993, 2953 and references cited therein.
52. Guette, J. P.; Spassky, N.; Boucherot, D. Bull. Chem. Soc. Fr., 1972, 4217.
53. Nakajima, N.; Horita, K.; Abe, R Tetrahedron Lett., 1988, 29, 4139.
54. For a recent review of nucleophilic additions to chiral carbonyl compounds, see: Mengel, A.; Reiser, O. Chem. Rev. 1999, 99, 1191.
55. For examples, see: (a) Lee, A. W. M.; Martin, V. S.; Masamune, S.; Sharpless, K. B.; Walker, F. J. J. Am. Chem. Soc., 1982, 104, 3515;
(b) Lee, A. W. M. Magnetic Resonance in Chemistry, 1985, 23, 468.
56．毛建民，兰州大学硕士论文，1987年．
57. For a recent review of Mukaiyama aldol reaction, see: Mahrwald, R. Chem. Rev. 1999, 99, 1095.
58. For a review of directed aldol reaction, see: (a) Mukaiyama, T. Org. React., 1982, 28, 203. For the reports of isomerization of aldols through a retroaldol mechanism, see:
(b) Swiss, K. A.; Choi, W.-B.; Liotta, D. C.; Abdel-Magid, A. F.; Maryanoff, C. A. J. Org. Chem., 1991, 56, 5978;
(c) Aurrecoeches, J. M.; Fananas, R.; Arrate, M.; Gorgojo, J. M.; Aurrekoetxea, N. J. Org. Chem., 1999, 64, 1893;
(d) Mahrwald, R.; Costisella, B.; Gundogan, B. Synthesis, 1998, 262;
(e) Yang, W.; Digits, C. A.; Hatada, M.; Narula, S.; Rozamus, L. W.; Huestis, C. M.; Wong, J.; Dalgarno, D.; Holt, D. A. Org. Lett., 1999, 1, 2033;
(f) Kim, K. S.; Hong, S. D. Tetrahedron Lett., 2000, 41, 5909.
59. Anderson, G. D.; Powers, T. J.; Djerassi, C.; Fayos, J.; Clardy, J. J. Am. Chem. Soc., 1975, 97, 388.
60. (a)Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett., 1985, 26, 69；
(b)林国强，陈耀全，陈新滋，李月明．手性合成--不对称反应及其应用，科学出版社，北京，2000，p．105．
61．梁晓天，核磁共振-高分辨氢谱的解析和应用，科学出版社，北京，1976，233．
62. (a) Allevi, P.; Cajone, F.; Ciulfreda, P.; Anastasia, M. Tetrahedron Lett., 1995, 36, 1347;
(b) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett., 1990, 31, 945;
(c) Dana, G.; Danechpajouh, H. Bull. Soc. Chim. Fr., 1980, 395.
63. Nagaoka, H.; Miyaoka, H.; Miyakoshi, T.; Yamada, Y. J. Am. Chem. Soc., 1986, 108, 5019.
64. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3~(rd) ed. John Willey & Sons, 1991.
65. Brook, A. G.; Macrae, D.M. J Organomet. Chem., 1974, 77, C19.
66. Kohler, W.; Pfleiderer, W. Liebigs Ann. Chem., 1979, 1855.
67. Boron aldol reactions with α-silyloxy ketones have recently been reported: (a) Murga, J.; Falomir, E.; Carda, M.; Gonz(?)lez, F.; Marco, J. A. Organic Lett. 2001, 3, 901.
(b) Murga, J.; Falomir, E.; Gonz(?)lez, F.; Carda, M.; Marco, J. A. Tetrahedron 2002, 58, 9697.
68. Lithium and magnesium aldol reactions with α'-silyloxy ketones have been reported: Van Draanen, N. A.; Arseniyadis, S.; Crimmins, M. T.; Heathcock, C. H. J. Org. Chem. 1991, 56, 2499.
69. For the reports of isomerization of aldols through a retroaldol mechanism, see: (a) Nielsen, A. T.; Houlihan, W. J. Org. React. 1982, 16, 1.
(b) Kok, P.; Sinha, N. D.; Sandra, P.; de Clercq, P. J.; Vandewalle, M. E. Tetrahedron 1982, 38, 2279.
(c) Vekgova, H. Collect. Czech. Chem. Commun. 1986, 51, 930.
(d) Swiss, K. A.; Choi, W.-B.; Liotta, D. C.; Abdel-Magid, A. F.; Maryanoff, C. A. J. Org. Chem. 1991, 56, 5978.
(e) Hui, A.; Fairbanks, A. J.; Nash, R. J.; de Q. Lilley, P. M.; Storer, R.; Watkin, D. J.; Fleet, G. W. J. Tetrahedron Lett. 1994, 47, 8895.
(f) Seto, H.; Fujioka, S.; Kamiya, Y.; Yoshiya, S. Heterocycles 1998, 48, 2245.
(g) Mukaiyama, T.; Shiina, I.; Iwadare, H.; Saiton, M.; Nishimura, T.; Ohkawa, N.; Sakoh, H.; Nishimura, K.; Tani, Y.-i.; Hasegawa, M.; Yamada, K.; Saitoh, K. Chem. Eur. J. 1999, 5, 121.
(h) Aurrecoeches, J. M.; Fananas, R.; Arrate, M.; Gorgojo, J. M.; Aurrekoetxea, N. J. Org. Chem. 1999, 64, 1893.
(i) Mahrwald, R.; Costisella, B.; Gundogan, B. Synthesis 1998, 262.
(j) Yang, W.; Digits, C. A.; Hatada, M.; Narula, S.; Rozamus, L. W.; Huestis, C. M.; Wong, J.; Dalgarno, D.; Holt, D. A. Org. Lett. 1999, 1, 2033.
70. Zimmerman, H.; Traxler, M. J. Am. Chem. Soc. 1957, 79, 1920.
71. (a) Zhow, W. S.; Jiang, B.; Pan, X. F..J. Chem. Soc. Chem. Commu.; 1989, 612;
(b) Zhow, W. S.; Jiang, B.; Pan, X. F. Tetrahedron, 1990, 46, 3173.
1. Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; Oregan, M. J. Am. Chem. Soc. 1990, 112, 3875.
2. Fu, G. C.; Nguyen, S. T.; Grubbs, R.H. J. Am. Chem. Soc. 1993, 115, 9856.
3. Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R.H. Angew. Chem. Int. Ed. Engl. 1995, 34, 2039.
4. H(?)risson, J. L.; Chauvin, Y. Makromol. Chem. 1970, 141,161.
5. Villemin, D. Tetrahedron Lett. 1980, 21, 1715.
6. Couturier, J. L.; Paillet, C.; Leconte, M.; Basset, J. M.; Weiss, K. Angew. Chem. Int. Ed. Engl. 1992, 31,628.
7. a). Couturier, J. L.; Tanaka, K.; Leconte, M.; Basset, J. M.; Ollivier, J. Angew. Chem. Int. Ed. Engl. 1993, 32, 112.
b). Couturier, J. L.; Leconte, M. J. Organmet. Chem. 1993, 451, C7.
8. Leconte, M.; Pagano, S.; Mutch, A.; Lefebrve, F.; Basset, J.M. Bull. Soc. Chim. Fr. 1995, 132, 1069.
9. Nugent, W. A.; Feldman, J.; Calabrese, J. C. J. Am. Chem. Soc. 1995, 61, 7963.
10. Martinez, L.E.; Nugent, W. A.; Jacobsen, E.N. J. Org. Chem. 1996, 61, 7963.
11. Descotes, G.; Ramza, J.; Basset, J. M.; Pagano, S.; Gentil, E.; Banoub, J. Tetrahedron 1996, 52, 10903.
12. a). Junga, H.; Blechert, S. Tetrahedron Lett. 1993, 34, 3731.
b). Schneider, M. F.; Junga, H.; Blectert, S. Tetrahedron 1995, 51, 13003.
13. Fu, G. C.; Grubbs, R. H. J. Am. Soc. Chem. 1993, 115, 3800.
14. Barrett, A. G.; Baugh, S. P. D.; Gilbon, V. G.; Giles, M. R.; Marshall, E. L.; Procopiou, P.A. Chem. Commun. 1996, 2231.
15. Forbes, M. D. E.; Patton, J. T.; Myers, T. L; Maynard, H. D.; Smith, D. W.; Schulz, G. R.; Wangener, K.B. J. Am. Chem. Soc. 1992, 114, 10978.
16. Barrett, A. G.; Baugh, S. P. D.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1997, 155.
17. Fu, G. C.; Grubbs, R.H. J. Am. Soc. Chem. 1992, 114, 7324.
18. Fu, G. C.; Grubbs, R. H. J. Am. Soc. Chem. 1992,114, 5426.
19. Fujimura, O.; Fuand, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59,4029.
20. Shon, Y. S.; Lee, T. R. Tetrahedron Lett. 1997, 38,1283.
21. Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993,115, 9856.
22. Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997,119, 3887.
23. Furstner, A.; Ackermann, L.; Bedk, K.; Hori, H.; Koch, D.; Langermann, K.; Liebl,M.; Six, C.; Leitner, W. J. Am. Chem. Soc. 2001,123, 9000.
24.Zuercher, W. J.; Hashimoto, M.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118,6634.
25. Trevitt, M.; Gouverneur, V. Tetrahedron Lett. 1999,40,7333.
26. Leconte, M.; Jourdan, I.; Pagano, S.; Lefebvre, F.; Basset, J. M. J. Chem. Soc.Chem. Commun. 1995,857.
27. a). Hanson, P. R.; Stoinova, D. S. Tetrahedron Lett. 1998, 39, 3939. b). Bujard,M.; Gouverneur, V.; Mioskowski, C. J. Org. Chem. 1999, 64,2119.
28. Hetherington, L.; Greedy, B.; Gouverneur, V. Tetrahedron 2000, 56,2053.
29. Louie, J.; Grubbs, R. H. Organometallics 2002,21,2153.
30. Huang, J.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. J. Am. Chem. Soc. 1999,121,2674.
31. Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999,40,2247.
32. Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 953.
33. Furstner, A.; Thiel, O. R.; Ackermann, L.; Schanz, H. L.; Nolan, S. P. J. Org.Chem. 2000, 65,2204.
34. Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc.2000,122, 3783.
35. Spagnol, G.; Heck, M. P.; Nolan, S. P.; Mioskowski, C. Org. Lett. 2002,4,1767.
36. Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001,34,18.
37.a). Fujimura, O.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 2499. b).Alexander, J. B.; La, D. S.; Cefalo, D. R. J. Am. Chem. Soc. 1998, 120, 4041.c). La, D. S.; Alexander, J. B.; Cefalo, D. R. J. Am. Chem. Soc. 1998, 120, 9720.
d). Fujimura, O.; Grubbs, R.H. J. Org. Chem. 1998, 63, 824.
38. a). Harrity, J. P. A.; La, D. S.; Cefalo, D.R. J. Am. Chem. Soc. 1998, 120, 2343.
b). Harrity, J. P. A.; Visser, M. S.; Gleason, J.D. J. Am. Chem. Soc. 1997, 119, 1488.
39. a) Kiely, A. F.; Jerneliu, J. A.; Schrock, R. R.; Hoveyda, A.H. J. Am. Chem. Soc. 2002, 124, 2868.
b). Dolman, S. J.; Sattely, E. S.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 2002, 124, 6991.
40. Nguyen, S. T.; Grubbs, R.H. J. Organomet. Chem. 1995, 497, 195.
41. Ahmed, M.; Barrett, A. G. M.; Braddock, D. C.; Cramp, S. M.; Procopiou, P. A. Tetrahedron Lett. 1999, 40, 8657.
42. Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoverda, A.H. J. Am. Chem. Soc. 1999, 121,791.
43. Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoverda, A.H. J. Am. Chem. Soc. 2000, 122, 8168.
44. Qingwei, Y. Angew, Chem. Int. Ed. 2000, 39, 3896.
45. Sch(u|¨)er, S. C.; Gessler, S.; Buschmann, N.; Blechert, S. Angew, Chem. Int. Ed. 2000, 39, 3898.
46. a). Crimmins, M. T.; King, B.W. J. Org. Chem. 1996, 61, 4192.
b). Martinez, L. E.; Nugent, W. A.; Jacobsen, E.N. J. Org. Chem. 1996, 61, 7963.
47. Dyatkin, A.B. Tetrahedron Lett. 1997, 38, 2065.
48. Overkleeft, H. S.; Pandit, U.K. Tetrahedron Lett. 1996, 37, 547.
49. Chang, S.; Grubbs, R. H. J. Org. Chem. in press.
50. Miller, S. J.; Kim, S.-H.; Chen, Z.-R.;. Grubbs, R.H.J. Am. Chem. Soc. 1995, 117,2108.
51. Diedrichs, N.; Westermann, B. Synlett 1999, 1127.
52. Tarling, C. A.; Holmes, A. B.; Markwell, R. E.; Pearson, N. D. J. Chem. Soc. Perkin Trans. l 1999, 1695.
53. Grossmith, C. E.; Senia, F.; Wagner, J. Synlett 1999, 1660.
54. Cook, G. R.; Shanker, P. S.; Peterson, S. L. Org. Lett. 1999, 1,615.
55. Delgado, M.; Martin, J.D. J. Org. Chem. 1999, 64, 4798.
56. Oguri, H.; Sasaki, S. Y.; Oishi, T.; Hirama, M. Tetrahrdron Lett. 1999, 40, 5405.
57. Van Hooft, P. A. V.; Leeuwenburgh, M. A.; Overkleeft, H. S.; Van der Marel, G. A.; Van Boeckel, C. A. A.; Van Boom, J.H. Tetrahedron Lett. 1999, 40, 4267.
58. Crimmins, M. T.; Chow, A.L. J. Am. Chem. Soc. 1999, 121, 5653.
59. Edwards, S. D.; Lewis, T.; Taylor, R. J.K. Tetrahedron Lett. 1999, 40, 3553.
60. Crimmins, M. T.; Emmitte, K.A. Org. Lett. 1999, 1, 2029.
61. F(u|¨)rstner, A.; M(u|¨)ller, T. Synlett 1997, 1010.
62. Gedaeh, K.; Quitschalle, M.; Kalesse, M. Tetrahedron Lett. 1999, 40, 3553.
63. Quitschalle, M.; Kalesse, M. Tetrahedron Lett. 1999, 40, 7765.
64. F(u|¨)rstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942.
65. F(u|¨)rstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005.
66. Kim, S. H.; Figueroa, I.; Fuchs, P.L. Tetrahedron Lett. 1997, 38, 2601.
67. F(u|¨)rstner, A.; Thiel, O. R.; Kindler, N.; Bartkowska, B. J. Org. Chem. 2000, 65, 7990.
68. Marsella, M.; Maynard, H.; Grubbs, R.H. Angew. Int. Ed. Engl. 1997, 36, 1101.
69. K(o|¨)nig, B.; Horn, C. Synlett 1996, 1013.
70. Huwe, C. M.; Velder, J.; Blechert, S. Angew. Chem. Int. Eng. Ed. 1996, 35, 2376.
71. Huwe, C. M.; Blechert, S. Synthesis 1997, 61.
72. Kinoshita, A.; Mori, M. Synlett 1994, 1020.
73. Kinoshita, A.; Mori, M. J. Org. Chem. 1996, 61, 8356.
74. Bentz, D.; Laschat, S. Synthesis 2000, 1766.
75. Kim, S.-H.; Bowden, N.; Grubbs, R.H. J. Am. Chem. Soc. 1994, 116, 10801.
76. Kim, S.-H.; Zuercher, W. J.; Bowden, N.; Grubbs, R.H. J.. Org. Chem. 1996, 61, 1073.
77. Reviews: a) Schuster, M., Blechert, S. Angew. Chem. Int. Ed. Engl. 1997, 36, 2036.
b) Armstrong, S.K. J. Chem. Soc. Perkin. Trans. l 1998, 371.
c) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 4651.
78. Numata, k Hokimoto and T.Katsuno, Chem. phaem. Bull., 1984, 32, 2815.
79. M. S. Buchanan and T. Hashimoto, Phytochemistry, 1995, 40, 1251.
80. K. H. Hollenbeak and M. E. Kuechne, Tetrahedron, 1974,30,2307.
81. V. L. Steven and A. Armstrong, J. Chem. Soc, Perkin Trans. 1, 1991, 667.
82. Gan Yonghong, Zhang Fangning and Pan Xinfu, Journal of Chemical Research,Synopses, 1999,8,488.
83. a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc, 1980,102, 5974; b) Wolloams,I. D.; Pedersen, S. F.; Sharpless, K. B. J. Am. Chem. Soc, 1984, 106, 6430; c) Rossiter, B. E. Chem. Ind. 1985,22(Catal. Org. react.), 295. (Review).
1. a) Nakamura, I. and Yamamoto, Y. Chem. Rev. 2004, 104, 2127;
b) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285;
c) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079;
d) Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev., 2007, 107, 174;
2. a) Meijere, A. D.; Zezschwitz, P.V.; Br(a|¨)se, S. Acc. Chem. Res. 2005, 38, 413;
b) Cacchi, S.; Fabrizi, G. Chem.Rev. 2005, 105, 2873;
c) Lunxiang Yin and Liebscher, J. Chem. Rev., 2007, 107, 133;
d) Denmark, S. E.and Regens, C. S. Acc. Chem. Res., 2008, 41, 1486;
e) W(u|¨)rtz, S. and Glorius, F. Acc. Chem. Res., 2008, 41,1523;
f) Gregory, C. Fu. Acc. Chem. Res., 2008, 41, 1555.
3. Previous reviews: a) C. Aubert; O. Buisine; M. Malacria, Chem.Rev. 2002, 102, 813;
b) F. E. McDonald, Chem. Eur. J. 1999, 5, 3103;
c) M. Mendez, V. Mamane, A. F(u|¨)rstner, Chem Tracts 2003, 16, 397;
d) G. C. Lloyd-Jones, Org. Biomol. Chem. 2003, l, 215.
4. J. Blum, H. Beer-Kraft, Y. Badrieh, J. Org. Chem. 1995, 60, 5567.
5. N. Chatani, N. Furukawa, H. Sakurai, S.Murai, Organometallics. 1996, 15, 901.
6. A. F(u|¨)rstner, H. Szillat, B. Gabor, R. Mynott, J. Am. Chem. Soc. 1998, 120, 8305.
7. a)A. F(u|¨)rstner, H. Szillat, F. Stelzer, J. Am. Chem. Soc. 2000, 122, 6785;
b) A. F(u|¨)rstner, H. Szillat, J. Am. Chem. Soc. 2001, 123, 11863.
8. a) C. Fernandez-Rivas, M. Mendez, A. M. Echavarren, J. Am. Chem. Soc. 2000, 122, 1221;
b) C. Fernandez-Rivas, M. Mendez, A. M. Echavarren, J. Org. Chem. 2002, 67, 5197; For a review see: M. Mendez, A. M. Echavarren, Eur. J. Org. Chem. 2002, 15.
9. a) M. Mendez, M. P. Munoz, A. M. Echavarren, J. Am. Chem. Soc. 2000, 122, 11549;
b) M. Mendez, M. P. Munoz, C. Nevado, D. J. Cardenas, A. M. Echavarren, J. Am. Chem. Soc. 2001, 123, 10511;
c) M. P. Munoz, M. Mendez, C. Nevado, D. J. Cardenas, A. M. Echavarren, Synthesis 2003, 2898.
10. a) Jim(?)nez-N(?)ez, E.; Echavarren, A.M. Chem. Rev. 2008, 108, 3326;
b) Michelet, V.; Toullec, P.Y.; Gen(?)t, J.-P. Angew. Chem., Int. Ed. 2008, 47, 4268;
c) Nieto-Oberhuber, C.; L(?)pez, S.; Jim(?)nez-N(?)ez, E.; Echavarren, A. M. Chem. Eur. J. 2006, 12, 5916;
d) Zhang, L.; Sun, J.; Kozmin, S. A. Adv. Synth. Catal. 2006, 348, 2271.
11. For select reviews on metal catalyzed isomerization of enynes, see: a) Ma, S.; Yu, S.; Gu, Z. Angew. Chem., Int. Ed. 2006, 45, 200;
b) Bruneau, C. Angew. Chem., Int. Ed. 2005, 44, 2328;
c) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317;
d) A(n|¨)orbe, L.; Dominguez, G; P(?)rez-Castells, J. Chem. Eur. J. 2004, 10, 4938;
e) Echavarren, A. M.; Nevado, C. Chem. Soc. Rev. 2004, 33, 431;
f) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813; For select examples, see:
g) Toullec, P. Y.; Genin, E.; Leseurre, L.; Genet, J.-P.; Michelet, V. Angew. Chem., Int. Ed. 2006, 45, 7427;
h) Cho, E. J.; Kim, M.; Lee, D. Org. Lett. 2006, 8, 5413;
i) Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2004, 126, 11806;
i) Mendez, M.; Munoz, M. P.; Nevado, C.; Cardenas, D. J.; Echavarren, A. M. J. Am. Chem. Soc. 2001, 123, 10511;
k)Chatani, N.; Kataoka, K.; Murai, S. J. Am. Chem. Soc. 1998, 120, 9104.
12. a)#12
b) Nieto-Oberhuber, C.; L(?)pez, S.; Echavarren, A. M. J. Am. Chem. Soc. 2005, 127, 6178;
c) F(u|¨)rstner, A.; Davies, P. W.; Gress, T. J. Am. Chem. Soc. 2005, 127, 8244.
13. F(u|¨)rstner, A.; Stimson, C. C. Angew. Chem., Int. Ed. 2007, 46, 8845.
14. a) Fern(?)ndez-Rivas, C.; M(?)ndes, M.; Nieto-Oberhuber, C.; Echavarren, A. M. J. Org. Chem. 2002, 67, 5197;
b) Fern(?)ndez-Rivas, C.; M(?)ndes, M.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 1221.
15. a)#12
b) M(?)ndez, M.; Mu(?)oz, M. P.; Echavarren, A. M. J.. Am. Chem. Soc. 2000, 122, 11549.
16. Jim(?)nez-N(?)ez, E.; Claverie, C. K.; Nieto-Oberhuber, C.; Echavarren, A. M. Angew. Chem., Int. Ed. 2006, 45, 5452.
17. (a) Correa, A.; Marion, N.; Fensterbank, L.; Malacria, M.; Nolan, S. P.; Cavallo, L. Angew. Chem., Int. Ed. 2008, 47, 718;
b) F(u|¨)rstner, A.; Davies, P. W. Angew. Chem. Int. Ed. 2007, 46, 3410;
c) Marion, N.; Nolan, S. P. Angew. Chem., Int. Ed. 2007, 46, 2750;
d) Marco-Contelles, J.; Soriano, E. Chem. Eur. J. 2007, 13, 1350;
e) Valentin, R. J. Org. Chem. 1984, 49, 950;
f) Mainetti, E.; Mouri(?)s, V.; Dhimane, A.-L.; Fensterbank, V.; Malacria, M. J. Am. Chem. Soc. 2004, 126, 8656;
h) Manane. V.; Gress, T.; Krause, H.; F(u|¨)rstner, A. J. Am. Chem. Soc. 2004, 126, 8654.
18. a) Ji, K.-G.; Shu, X.-Zh.; Chen, J.; Zhao, Sh.-Ch.; Zheng, Zh.-J.; Lu, L.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2008, 10, 3919;
b) Shu, X.-Zh.; Liu, X.-Y.; Ji, K.-G.; Xiao, H.-Q.; Liang, Y.-M. Chem. Eur. J. 2008, 14, 5282;
c) Ji, K.-G.; Shen, Y.-W.; Shu, X.-Zh.; Xiao, H.-Q.; Bian, Y.-J.; Liang, Y.-M. Adv. Synth. Catal. 2008, 350, 1275;
d) Shu, X.-Zh.; Liu, X.-Y.; Xiao, H.-Q.; Ji, K.-G.; Guo, L.-N.; Liang, Y.-M. Adv. Synth. Catal. 2008, 350, 243;
e) Shu, X.-Zh.; Liu, X.-Y.; Xiao, H.-Q.; Ji, K.-G.; Guo, L.-N.; Qi, Ch.-Z.; Liang, Y.-M. Adv. Synth. Catal. 2007, 349, 2493.
19. a) F(u|¨)rstner, A.; Davies, P. W. J. Am. Chem. Soc. 2005, 127, 15024;
b) F(u|¨)rstner, A.; Davies, P. W.; Gress, T. J. Am. Chem. Soc. 2005, 127, 8244;
c) F(u|¨)rstner, A.; Aissa, C. J. Am. Chem. Soc. 2006, 128, 6306;
d) Sohel, S. M. A.; Lin, S.-H.; Liu, R.-S.; Synlett 2008, 5, 745;
e) Das, A.; Liao, H.-H.; Liu, R.-S. J. Org. Chem. 2007, 72, 9214.
20. Li, G.; Zhang, G.; Zhang, L. J. Am. Chem. Soc. 2008, 130, 3740.
21. a) Barluenga, J.; Fernandez-Rodriguez, M. A.; Garcia-Garcia, P.; Aguilar, E. J. Am. Chem. Soc. 2008, 130, 2764;
b) Barluenga, J.; Riesgo, L.; Vicente, R.; Lopez, L. A.; Tomas, M. J. Am. Chem. Soc. 2007, 129, 7772.
22. For select examples on[1,3]-OAt shift, see: a) Zhang, G.; Catalano, V. J.; Zhang, L. J. Am. Chem. Soc. 2007, 129, 11358;
b) Marion, N.; Diez-Gonz(?)lez, S.; Fr(?)mont de, P.; Noble, A. R.; Nolan, S. P. Angew. Chem., Int. Ed 2006, 45, 3647;
c) Zhang, L.; Wang, S. J. Am. Chem. Soc. 2006, 128, 1442;
d) Zhang, L. J. Am. Chem. Soc. 2005, 127, 16804.
23. For examples of aromatization in the air, see: a) Kadzimirsz, D.; Hildebrandt, D.; Merz, K.; Dyker, G. Chem. Commun. 2006, 661;
b) Abbiati, G.; Arcadi, A.; Bianchi, G.; Giuseppe, S. D.; Marinelli, F.; Rossi, E. J. Org. Chem. 2003, 68, 6959;
c)Also see ref(13).
2. Buchel, K. H. Chemistry of Pesticides, John Willey &Sons, New York, 1983, p. 6.
3．樊德方，黄幸舒，农药的污染与防治，科学出版社，北京，1982，p．2．
4．相关综述，参考文献[1]，p．597。
5. Michell, J. W.; Mandava, N.; Worley, J. F.; Plimmer, J. R.; Smith, M. V. Nature, 1970, 225, 1065;
6. Grove, M. D.; Spence, G. F.; Rohwedder, W. K.; Mandava, N.; Worley, J. F.; Warthen, J. D. Jr.; Stefrens, G. L.; Flippen-Anderson, J. L.; Cook, J. C. Jr. Nature, 1979, 281,216;
7. Yokota, T. Tetrahedron Lett., 1982, 23, 1275.
8. Maeda, E. Physiol. Plant., 1965, 18, 813;
9. Ikeda, M. Agrio. Biol. Chem., 1983, 42, 655;
10. Baba, T. Agrio. Biol. Chem., 1983, 47, 659;
11. Yokota, T.; Baba, T. Agrio. Biol. Chem., 1983, 47, 1409;
12. Takatsuto, S. "25th Symposium on the Chemistry of Natural Products, Tokyo ", 1982, 290;
13. Takatsuto, S. J.. Chromatogr, 1982, 233;
14. Abe, H. Agrio. Biol. Chem.,1984, 48, 2171.
15. Schneide, J. A. Tetrahedron Lett., 1983, 24, 3859.
16. Khripach, V. A.; Zhabinskii, V. N.; de Groot, A. E. Brassinosteroids, A New Class of Plant Hormones. Academic Press, 1999, p19.
17. Abe, H.; in Brassinosteroids; Chemistry, Bioactivity, and Appllications, ed. Cutler, H. G.; Yokota, T.; Adam, G.; American Chemical Society, Washington, 1991, p. 200.;
18. Abe, H.; Nakamura, K.; Morishita, T.; Uchiyama, M.; Takatsuto, S.; Ikekawa, N. Agric. Biol. Chem., 1984, 48, 1103;
19. Abe, H.; Takatsuro, S.; Nakayama, M.; Yokota, T.; Biosci. Biotechnol. Biochem., 1995, 59, 176;
20. Schmidt, J.; Schmidt, J.; Spengler, B.; Yokota, Y.; Nakayama, M.; Takatsuto, S.; Voigt, B.; Adam, G. Phytochemistry, 1995, 38, 1095;
21. Yakota, T.; Nakayama, M.; Wakisaka, T.; Schmidt, J.; Adam, G. Biosci. Biotechnol. Biochem., 1994, 58, 1183;
22. Suzuki, Y.; Yamaguchi, I.; Yokota, T.; Takahashi, N. Agric. Biol. Chem., 1986, 50, 3133;
23. Gamoh, K.; Okamoto, N.; Takatsuto, S.; Tcjima, I. Anal, Chim. Atca, 1990, 228, 101;
24. Abe, H.; Honjo, C.; Kyokawa, Y.; Asakawa, S.; Natsume, M.; Narushima, M. Biosci. Biotechnol. Biochem., 1994, 58, 986;
25. Asakawa, S.; Abe, H.;Kyokawa, Y.; Nakamura, S.; Natsume, M. Biosci. Biotechnol. Biochem., 1994, 58, 219;
26. Ikeda, M.; Takatsuto, S.; Sassa, T.; Ikekawa, N.; Nukima, M. Agric. Biol. Chem., 1983, 47, 655;
27. Arima, M.; Yokota, T.; Takahashi, N. Phytochemistry, 1984, 23, 1587.
28. Abe, H.; Morishita, T.; Marumo, S.; Munakata, K.; Takatsuto, S.; Idikawa, N. Agric. Biol. Chem. 1982, 46, 2609.
29. Abe, H.; Morishita, T.; Uchiyama, M.; Takatsuto, S.; Ikekawa, N.; Ikeda, M.; Sassa, T.; Kitsuwa, T.; Marumo, S. Experientia, 1983, 39, 351.
30. Yokota, T.; Morita, M.; Takahashi, N. Agric. Biol. Chem., 1995, 40, 907.
31. Yokota, T.; Koba, S.; Kim, S.-K.; Tskatsuto, S.; Ikekawa, N.; Sakakioara, M.; Okada, K.; M. K.; Takahashi, N. Agric. Biol. Chem., 1987, 51, 1625.
32. Yokota, T.; Kim, S.-K.; Ko, Y.; Ogino, Y.; Takahashi, N.; in Conjugated plant hormones, structure metabolism and function, eds. Schreiber, K.; Sutte, H. R.; Sembdner, G. VEG Deuchter Verlag der wissenschtten, 1987, p-288.
33. Kim, S.-K.; Yokota, T.; Takahashi, N. Agric. Biol. Chem., 1987, 51, 2303.
34. Kim, S.-K.; in Brassinosteroids Chemistry, Bioactivity, and Applications, cd. Cutler, H. G.; Yokota, T.; Adam, G.; American Chemical Society, Washington, 1991, p.26.
35. Ikekawa, N.; Takatsuto, S.; Kitsuwa, T.; Saito, H.; Morishita, T.; Abe, H. J. Chromatogr., 1984, 290, 289.
36. Morishita, T.; Abe, H.; Uchiyama, M.; Marumo, S.; Takatsuto, S.; Ikekawa, N.; Phytochemistry, 1983, 22, 1051.
37. Abe, H.; Morishita, T.; chiyama, M.; Takatsuto, S.; Ikekawa, N.; Agric. Biol. Chem., 1994, 48, 2171.
38. Suzuki, Y.; Yamaguchi, I.; Takahashi, N. Agric. Biol. Chem., 1985, 49, 49.
39. Yokota, T.; Arima, M.; Tal mashi, N.; Takatsuto, B.; Ikekawa, N.; Takematsu, T. Agric. Biol. Chem., 1983, 47, 2419.
40. Yokota, T.; Kim, S.-K.; Fuk, Y.; Takahashi, N.; Takeuchi, Y.; Takematsu, T. Phytochemistry, 1987, 25, 503.
41. Takatsuto, S. Tetrahedron Lett., 1983, 24, 1173.
42. Mori, K. Agric. Biol. Chem., 1983, 47, 97.
43. Sakakibara, M.; Mori, K.; Agric. Biol. Chem., 1983, 47, 336.
44. For reviews, see: (a) Back, T. G.; Baron, D. L.; Lou, W.; Nakajima, S. K. J. Org. Chem., 1997, 62, 1179-1182;
(b) Back, T. G.; Krishna, M. V. Can. J. Chem., 1993, 71, 156-163;
(c) Back, T. G.; Janzen, L.; Nakajima, S. K.; Pharis, R. P. J. Org. Chem., 1999, 64, 5494-5498;
(d) Back, T. G.; Janzen, L.; Nakajima, S. K.; Pharis, R. P. J. Org. Chem. 2000, 65, 3047-3052;
(e) Baron, D. L.; Luo, W.; Janzen, L.; Pharis, R. P.; Back, T. G. Phytochemistry, 1998, 49, 1849-1858;
(f) Fujioks, S.; Noguchi, T.; Takatsuto, S.; Yoshida, S. Phytochemistry, 1998, 49, 1841-1848;
(g) Fujioks, S.; Noguchi, T.; Watanabe, T.; Takatsuto, S.; Yoshida, S. Phytoche mistry, 2000, 53, 549-552;
(h) Fujioks, S.; Sakurai, A.; Natural Product Reports, 1997, 14, 1-10;
(i) Sung, G. C. Y.;; Janzen, L.; Pharis, R. P.; Back, T. G. Phytochemistry, 2000, 55, 121-126.
45. Mori, K,; Takeuchi, T. Liebigs Ann. Chem., 1988, 815.
46. (a) Honda, T.; Keino, K.; Tsubuki, M. J. Chem. Soc., Chem. Commun., 1990, 650;
(b) Tsubuki, M.; Keino, K.; Honda, T. J. Chem. Soc.,Perkin Trans 1,, 1992,2643.
47. Takatsuto, S.; Yazaka, N.; Ikekawa, N. Phytochemistry, 1984, 23, 525.
48. Zhou, W. S.; Huang, L. F.; Sun, L. Q.; Pan, X. F. J. Chem. Soc., Perkin Trans 1, 1986, 108, 7055.
49. Hayashi, S.; Hohjoh, T.; Shida, A.; Ikekawa, N. Eur Pat. Appl. EP, 282 984(CA: 110, 95 639s).
50. Huang, L. F.; Zhou, W. S. J. Chem. Soc., Perkin Trans 1, 1994, 3579.
51. (a) Li, W. D. Z.; Li, Y.; Li, Y. L. Tetrahedron Lett., 1999, 40, 966;
(b) Li, Y. L.; Li, W. D.; Li, Y. J. Chem. Soc. Perkin Trans I, 1993, 2953 and references cited therein.
52. Guette, J. P.; Spassky, N.; Boucherot, D. Bull. Chem. Soc. Fr., 1972, 4217.
53. Nakajima, N.; Horita, K.; Abe, R Tetrahedron Lett., 1988, 29, 4139.
54. For a recent review of nucleophilic additions to chiral carbonyl compounds, see: Mengel, A.; Reiser, O. Chem. Rev. 1999, 99, 1191.
55. For examples, see: (a) Lee, A. W. M.; Martin, V. S.; Masamune, S.; Sharpless, K. B.; Walker, F. J. J. Am. Chem. Soc., 1982, 104, 3515;
(b) Lee, A. W. M. Magnetic Resonance in Chemistry, 1985, 23, 468.
56．毛建民，兰州大学硕士论文，1987年．
57. For a recent review of Mukaiyama aldol reaction, see: Mahrwald, R. Chem. Rev. 1999, 99, 1095.
58. For a review of directed aldol reaction, see: (a) Mukaiyama, T. Org. React., 1982, 28, 203. For the reports of isomerization of aldols through a retroaldol mechanism, see:
(b) Swiss, K. A.; Choi, W.-B.; Liotta, D. C.; Abdel-Magid, A. F.; Maryanoff, C. A. J. Org. Chem., 1991, 56, 5978;
(c) Aurrecoeches, J. M.; Fananas, R.; Arrate, M.; Gorgojo, J. M.; Aurrekoetxea, N. J. Org. Chem., 1999, 64, 1893;
(d) Mahrwald, R.; Costisella, B.; Gundogan, B. Synthesis, 1998, 262;
(e) Yang, W.; Digits, C. A.; Hatada, M.; Narula, S.; Rozamus, L. W.; Huestis, C. M.; Wong, J.; Dalgarno, D.; Holt, D. A. Org. Lett., 1999, 1, 2033;
(f) Kim, K. S.; Hong, S. D. Tetrahedron Lett., 2000, 41, 5909.
59. Anderson, G. D.; Powers, T. J.; Djerassi, C.; Fayos, J.; Clardy, J. J. Am. Chem. Soc., 1975, 97, 388.
60. (a)Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett., 1985, 26, 69；
(b)林国强，陈耀全，陈新滋，李月明．手性合成--不对称反应及其应用，科学出版社，北京，2000，p．105．
61．梁晓天，核磁共振-高分辨氢谱的解析和应用，科学出版社，北京，1976，233．
62. (a) Allevi, P.; Cajone, F.; Ciulfreda, P.; Anastasia, M. Tetrahedron Lett., 1995, 36, 1347;
(b) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett., 1990, 31, 945;
(c) Dana, G.; Danechpajouh, H. Bull. Soc. Chim. Fr., 1980, 395.
63. Nagaoka, H.; Miyaoka, H.; Miyakoshi, T.; Yamada, Y. J. Am. Chem. Soc., 1986, 108, 5019.
64. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3~(rd) ed. John Willey & Sons, 1991.
65. Brook, A. G.; Macrae, D.M. J Organomet. Chem., 1974, 77, C19.
66. Kohler, W.; Pfleiderer, W. Liebigs Ann. Chem., 1979, 1855.
67. Boron aldol reactions with α-silyloxy ketones have recently been reported: (a) Murga, J.; Falomir, E.; Carda, M.; Gonz(?)lez, F.; Marco, J. A. Organic Lett. 2001, 3, 901.
(b) Murga, J.; Falomir, E.; Gonz(?)lez, F.; Carda, M.; Marco, J. A. Tetrahedron 2002, 58, 9697.
68. Lithium and magnesium aldol reactions with α'-silyloxy ketones have been reported: Van Draanen, N. A.; Arseniyadis, S.; Crimmins, M. T.; Heathcock, C. H. J. Org. Chem. 1991, 56, 2499.
69. For the reports of isomerization of aldols through a retroaldol mechanism, see: (a) Nielsen, A. T.; Houlihan, W. J. Org. React. 1982, 16, 1.
(b) Kok, P.; Sinha, N. D.; Sandra, P.; de Clercq, P. J.; Vandewalle, M. E. Tetrahedron 1982, 38, 2279.
(c) Vekgova, H. Collect. Czech. Chem. Commun. 1986, 51, 930.
(d) Swiss, K. A.; Choi, W.-B.; Liotta, D. C.; Abdel-Magid, A. F.; Maryanoff, C. A. J. Org. Chem. 1991, 56, 5978.
(e) Hui, A.; Fairbanks, A. J.; Nash, R. J.; de Q. Lilley, P. M.; Storer, R.; Watkin, D. J.; Fleet, G. W. J. Tetrahedron Lett. 1994, 47, 8895.
(f) Seto, H.; Fujioka, S.; Kamiya, Y.; Yoshiya, S. Heterocycles 1998, 48, 2245.
(g) Mukaiyama, T.; Shiina, I.; Iwadare, H.; Saiton, M.; Nishimura, T.; Ohkawa, N.; Sakoh, H.; Nishimura, K.; Tani, Y.-i.; Hasegawa, M.; Yamada, K.; Saitoh, K. Chem. Eur. J. 1999, 5, 121.
(h) Aurrecoeches, J. M.; Fananas, R.; Arrate, M.; Gorgojo, J. M.; Aurrekoetxea, N. J. Org. Chem. 1999, 64, 1893.
(i) Mahrwald, R.; Costisella, B.; Gundogan, B. Synthesis 1998, 262.
(j) Yang, W.; Digits, C. A.; Hatada, M.; Narula, S.; Rozamus, L. W.; Huestis, C. M.; Wong, J.; Dalgarno, D.; Holt, D. A. Org. Lett. 1999, 1, 2033.
70. Zimmerman, H.; Traxler, M. J. Am. Chem. Soc. 1957, 79, 1920.
71. (a) Zhow, W. S.; Jiang, B.; Pan, X. F..J. Chem. Soc. Chem. Commu.; 1989, 612;
(b) Zhow, W. S.; Jiang, B.; Pan, X. F. Tetrahedron, 1990, 46, 3173.
1. Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; Oregan, M. J. Am. Chem. Soc. 1990, 112, 3875.
2. Fu, G. C.; Nguyen, S. T.; Grubbs, R.H. J. Am. Chem. Soc. 1993, 115, 9856.
3. Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R.H. Angew. Chem. Int. Ed. Engl. 1995, 34, 2039.
4. H(?)risson, J. L.; Chauvin, Y. Makromol. Chem. 1970, 141,161.
5. Villemin, D. Tetrahedron Lett. 1980, 21, 1715.
6. Couturier, J. L.; Paillet, C.; Leconte, M.; Basset, J. M.; Weiss, K. Angew. Chem. Int. Ed. Engl. 1992, 31,628.
7. a). Couturier, J. L.; Tanaka, K.; Leconte, M.; Basset, J. M.; Ollivier, J. Angew. Chem. Int. Ed. Engl. 1993, 32, 112.
b). Couturier, J. L.; Leconte, M. J. Organmet. Chem. 1993, 451, C7.
8. Leconte, M.; Pagano, S.; Mutch, A.; Lefebrve, F.; Basset, J.M. Bull. Soc. Chim. Fr. 1995, 132, 1069.
9. Nugent, W. A.; Feldman, J.; Calabrese, J. C. J. Am. Chem. Soc. 1995, 61, 7963.
10. Martinez, L.E.; Nugent, W. A.; Jacobsen, E.N. J. Org. Chem. 1996, 61, 7963.
11. Descotes, G.; Ramza, J.; Basset, J. M.; Pagano, S.; Gentil, E.; Banoub, J. Tetrahedron 1996, 52, 10903.
12. a). Junga, H.; Blechert, S. Tetrahedron Lett. 1993, 34, 3731.
b). Schneider, M. F.; Junga, H.; Blectert, S. Tetrahedron 1995, 51, 13003.
13. Fu, G. C.; Grubbs, R. H. J. Am. Soc. Chem. 1993, 115, 3800.
14. Barrett, A. G.; Baugh, S. P. D.; Gilbon, V. G.; Giles, M. R.; Marshall, E. L.; Procopiou, P.A. Chem. Commun. 1996, 2231.
15. Forbes, M. D. E.; Patton, J. T.; Myers, T. L; Maynard, H. D.; Smith, D. W.; Schulz, G. R.; Wangener, K.B. J. Am. Chem. Soc. 1992, 114, 10978.
16. Barrett, A. G.; Baugh, S. P. D.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1997, 155.
17. Fu, G. C.; Grubbs, R.H. J. Am. Soc. Chem. 1992, 114, 7324.
18. Fu, G. C.; Grubbs, R. H. J. Am. Soc. Chem. 1992,114, 5426.
19. Fujimura, O.; Fuand, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59,4029.
20. Shon, Y. S.; Lee, T. R. Tetrahedron Lett. 1997, 38,1283.
21. Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993,115, 9856.
22. Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997,119, 3887.
23. Furstner, A.; Ackermann, L.; Bedk, K.; Hori, H.; Koch, D.; Langermann, K.; Liebl,M.; Six, C.; Leitner, W. J. Am. Chem. Soc. 2001,123, 9000.
24.Zuercher, W. J.; Hashimoto, M.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118,6634.
25. Trevitt, M.; Gouverneur, V. Tetrahedron Lett. 1999,40,7333.
26. Leconte, M.; Jourdan, I.; Pagano, S.; Lefebvre, F.; Basset, J. M. J. Chem. Soc.Chem. Commun. 1995,857.
27. a). Hanson, P. R.; Stoinova, D. S. Tetrahedron Lett. 1998, 39, 3939. b). Bujard,M.; Gouverneur, V.; Mioskowski, C. J. Org. Chem. 1999, 64,2119.
28. Hetherington, L.; Greedy, B.; Gouverneur, V. Tetrahedron 2000, 56,2053.
29. Louie, J.; Grubbs, R. H. Organometallics 2002,21,2153.
30. Huang, J.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. J. Am. Chem. Soc. 1999,121,2674.
31. Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999,40,2247.
32. Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 953.
33. Furstner, A.; Thiel, O. R.; Ackermann, L.; Schanz, H. L.; Nolan, S. P. J. Org.Chem. 2000, 65,2204.
34. Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc.2000,122, 3783.
35. Spagnol, G.; Heck, M. P.; Nolan, S. P.; Mioskowski, C. Org. Lett. 2002,4,1767.
36. Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001,34,18.
37.a). Fujimura, O.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 2499. b).Alexander, J. B.; La, D. S.; Cefalo, D. R. J. Am. Chem. Soc. 1998, 120, 4041.c). La, D. S.; Alexander, J. B.; Cefalo, D. R. J. Am. Chem. Soc. 1998, 120, 9720.
d). Fujimura, O.; Grubbs, R.H. J. Org. Chem. 1998, 63, 824.
38. a). Harrity, J. P. A.; La, D. S.; Cefalo, D.R. J. Am. Chem. Soc. 1998, 120, 2343.
b). Harrity, J. P. A.; Visser, M. S.; Gleason, J.D. J. Am. Chem. Soc. 1997, 119, 1488.
39. a) Kiely, A. F.; Jerneliu, J. A.; Schrock, R. R.; Hoveyda, A.H. J. Am. Chem. Soc. 2002, 124, 2868.
b). Dolman, S. J.; Sattely, E. S.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 2002, 124, 6991.
40. Nguyen, S. T.; Grubbs, R.H. J. Organomet. Chem. 1995, 497, 195.
41. Ahmed, M.; Barrett, A. G. M.; Braddock, D. C.; Cramp, S. M.; Procopiou, P. A. Tetrahedron Lett. 1999, 40, 8657.
42. Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoverda, A.H. J. Am. Chem. Soc. 1999, 121,791.
43. Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoverda, A.H. J. Am. Chem. Soc. 2000, 122, 8168.
44. Qingwei, Y. Angew, Chem. Int. Ed. 2000, 39, 3896.
45. Sch(u|¨)er, S. C.; Gessler, S.; Buschmann, N.; Blechert, S. Angew, Chem. Int. Ed. 2000, 39, 3898.
46. a). Crimmins, M. T.; King, B.W. J. Org. Chem. 1996, 61, 4192.
b). Martinez, L. E.; Nugent, W. A.; Jacobsen, E.N. J. Org. Chem. 1996, 61, 7963.
47. Dyatkin, A.B. Tetrahedron Lett. 1997, 38, 2065.
48. Overkleeft, H. S.; Pandit, U.K. Tetrahedron Lett. 1996, 37, 547.
49. Chang, S.; Grubbs, R. H. J. Org. Chem. in press.
50. Miller, S. J.; Kim, S.-H.; Chen, Z.-R.;. Grubbs, R.H.J. Am. Chem. Soc. 1995, 117,2108.
51. Diedrichs, N.; Westermann, B. Synlett 1999, 1127.
52. Tarling, C. A.; Holmes, A. B.; Markwell, R. E.; Pearson, N. D. J. Chem. Soc. Perkin Trans. l 1999, 1695.
53. Grossmith, C. E.; Senia, F.; Wagner, J. Synlett 1999, 1660.
54. Cook, G. R.; Shanker, P. S.; Peterson, S. L. Org. Lett. 1999, 1,615.
55. Delgado, M.; Martin, J.D. J. Org. Chem. 1999, 64, 4798.
56. Oguri, H.; Sasaki, S. Y.; Oishi, T.; Hirama, M. Tetrahrdron Lett. 1999, 40, 5405.
57. Van Hooft, P. A. V.; Leeuwenburgh, M. A.; Overkleeft, H. S.; Van der Marel, G. A.; Van Boeckel, C. A. A.; Van Boom, J.H. Tetrahedron Lett. 1999, 40, 4267.
58. Crimmins, M. T.; Chow, A.L. J. Am. Chem. Soc. 1999, 121, 5653.
59. Edwards, S. D.; Lewis, T.; Taylor, R. J.K. Tetrahedron Lett. 1999, 40, 3553.
60. Crimmins, M. T.; Emmitte, K.A. Org. Lett. 1999, 1, 2029.
61. F(u|¨)rstner, A.; M(u|¨)ller, T. Synlett 1997, 1010.
62. Gedaeh, K.; Quitschalle, M.; Kalesse, M. Tetrahedron Lett. 1999, 40, 3553.
63. Quitschalle, M.; Kalesse, M. Tetrahedron Lett. 1999, 40, 7765.
64. F(u|¨)rstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942.
65. F(u|¨)rstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005.
66. Kim, S. H.; Figueroa, I.; Fuchs, P.L. Tetrahedron Lett. 1997, 38, 2601.
67. F(u|¨)rstner, A.; Thiel, O. R.; Kindler, N.; Bartkowska, B. J. Org. Chem. 2000, 65, 7990.
68. Marsella, M.; Maynard, H.; Grubbs, R.H. Angew. Int. Ed. Engl. 1997, 36, 1101.
69. K(o|¨)nig, B.; Horn, C. Synlett 1996, 1013.
70. Huwe, C. M.; Velder, J.; Blechert, S. Angew. Chem. Int. Eng. Ed. 1996, 35, 2376.
71. Huwe, C. M.; Blechert, S. Synthesis 1997, 61.
72. Kinoshita, A.; Mori, M. Synlett 1994, 1020.
73. Kinoshita, A.; Mori, M. J. Org. Chem. 1996, 61, 8356.
74. Bentz, D.; Laschat, S. Synthesis 2000, 1766.
75. Kim, S.-H.; Bowden, N.; Grubbs, R.H. J. Am. Chem. Soc. 1994, 116, 10801.
76. Kim, S.-H.; Zuercher, W. J.; Bowden, N.; Grubbs, R.H. J.. Org. Chem. 1996, 61, 1073.
77. Reviews: a) Schuster, M., Blechert, S. Angew. Chem. Int. Ed. Engl. 1997, 36, 2036.
b) Armstrong, S.K. J. Chem. Soc. Perkin. Trans. l 1998, 371.
c) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 4651.
78. Numata, k Hokimoto and T.Katsuno, Chem. phaem. Bull., 1984, 32, 2815.
79. M. S. Buchanan and T. Hashimoto, Phytochemistry, 1995, 40, 1251.
80. K. H. Hollenbeak and M. E. Kuechne, Tetrahedron, 1974,30,2307.
81. V. L. Steven and A. Armstrong, J. Chem. Soc, Perkin Trans. 1, 1991, 667.
82. Gan Yonghong, Zhang Fangning and Pan Xinfu, Journal of Chemical Research,Synopses, 1999,8,488.
83. a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc, 1980,102, 5974; b) Wolloams,I. D.; Pedersen, S. F.; Sharpless, K. B. J. Am. Chem. Soc, 1984, 106, 6430; c) Rossiter, B. E. Chem. Ind. 1985,22(Catal. Org. react.), 295. (Review).
1. a) Nakamura, I. and Yamamoto, Y. Chem. Rev. 2004, 104, 2127;
b) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285;
c) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079;
d) Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev., 2007, 107, 174;
2. a) Meijere, A. D.; Zezschwitz, P.V.; Br(a|¨)se, S. Acc. Chem. Res. 2005, 38, 413;
b) Cacchi, S.; Fabrizi, G. Chem.Rev. 2005, 105, 2873;
c) Lunxiang Yin and Liebscher, J. Chem. Rev., 2007, 107, 133;
d) Denmark, S. E.and Regens, C. S. Acc. Chem. Res., 2008, 41, 1486;
e) W(u|¨)rtz, S. and Glorius, F. Acc. Chem. Res., 2008, 41,1523;
f) Gregory, C. Fu. Acc. Chem. Res., 2008, 41, 1555.
3. Previous reviews: a) C. Aubert; O. Buisine; M. Malacria, Chem.Rev. 2002, 102, 813;
b) F. E. McDonald, Chem. Eur. J. 1999, 5, 3103;
c) M. Mendez, V. Mamane, A. F(u|¨)rstner, Chem Tracts 2003, 16, 397;
d) G. C. Lloyd-Jones, Org. Biomol. Chem. 2003, l, 215.
4. J. Blum, H. Beer-Kraft, Y. Badrieh, J. Org. Chem. 1995, 60, 5567.
5. N. Chatani, N. Furukawa, H. Sakurai, S.Murai, Organometallics. 1996, 15, 901.
6. A. F(u|¨)rstner, H. Szillat, B. Gabor, R. Mynott, J. Am. Chem. Soc. 1998, 120, 8305.
7. a)A. F(u|¨)rstner, H. Szillat, F. Stelzer, J. Am. Chem. Soc. 2000, 122, 6785;
b) A. F(u|¨)rstner, H. Szillat, J. Am. Chem. Soc. 2001, 123, 11863.
8. a) C. Fernandez-Rivas, M. Mendez, A. M. Echavarren, J. Am. Chem. Soc. 2000, 122, 1221;
b) C. Fernandez-Rivas, M. Mendez, A. M. Echavarren, J. Org. Chem. 2002, 67, 5197; For a review see: M. Mendez, A. M. Echavarren, Eur. J. Org. Chem. 2002, 15.
9. a) M. Mendez, M. P. Munoz, A. M. Echavarren, J. Am. Chem. Soc. 2000, 122, 11549;
b) M. Mendez, M. P. Munoz, C. Nevado, D. J. Cardenas, A. M. Echavarren, J. Am. Chem. Soc. 2001, 123, 10511;
c) M. P. Munoz, M. Mendez, C. Nevado, D. J. Cardenas, A. M. Echavarren, Synthesis 2003, 2898.
10. a) Jim(?)nez-N(?)ez, E.; Echavarren, A.M. Chem. Rev. 2008, 108, 3326;
b) Michelet, V.; Toullec, P.Y.; Gen(?)t, J.-P. Angew. Chem., Int. Ed. 2008, 47, 4268;
c) Nieto-Oberhuber, C.; L(?)pez, S.; Jim(?)nez-N(?)ez, E.; Echavarren, A. M. Chem. Eur. J. 2006, 12, 5916;
d) Zhang, L.; Sun, J.; Kozmin, S. A. Adv. Synth. Catal. 2006, 348, 2271.
11. For select reviews on metal catalyzed isomerization of enynes, see: a) Ma, S.; Yu, S.; Gu, Z. Angew. Chem., Int. Ed. 2006, 45, 200;
b) Bruneau, C. Angew. Chem., Int. Ed. 2005, 44, 2328;
c) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317;
d) A(n|¨)orbe, L.; Dominguez, G; P(?)rez-Castells, J. Chem. Eur. J. 2004, 10, 4938;
e) Echavarren, A. M.; Nevado, C. Chem. Soc. Rev. 2004, 33, 431;
f) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813; For select examples, see:
g) Toullec, P. Y.; Genin, E.; Leseurre, L.; Genet, J.-P.; Michelet, V. Angew. Chem., Int. Ed. 2006, 45, 7427;
h) Cho, E. J.; Kim, M.; Lee, D. Org. Lett. 2006, 8, 5413;
i) Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2004, 126, 11806;
i) Mendez, M.; Munoz, M. P.; Nevado, C.; Cardenas, D. J.; Echavarren, A. M. J. Am. Chem. Soc. 2001, 123, 10511;
k)Chatani, N.; Kataoka, K.; Murai, S. J. Am. Chem. Soc. 1998, 120, 9104.
12. a)#12
b) Nieto-Oberhuber, C.; L(?)pez, S.; Echavarren, A. M. J. Am. Chem. Soc. 2005, 127, 6178;
c) F(u|¨)rstner, A.; Davies, P. W.; Gress, T. J. Am. Chem. Soc. 2005, 127, 8244.
13. F(u|¨)rstner, A.; Stimson, C. C. Angew. Chem., Int. Ed. 2007, 46, 8845.
14. a) Fern(?)ndez-Rivas, C.; M(?)ndes, M.; Nieto-Oberhuber, C.; Echavarren, A. M. J. Org. Chem. 2002, 67, 5197;
b) Fern(?)ndez-Rivas, C.; M(?)ndes, M.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 1221.
15. a)#12
b) M(?)ndez, M.; Mu(?)oz, M. P.; Echavarren, A. M. J.. Am. Chem. Soc. 2000, 122, 11549.
16. Jim(?)nez-N(?)ez, E.; Claverie, C. K.; Nieto-Oberhuber, C.; Echavarren, A. M. Angew. Chem., Int. Ed. 2006, 45, 5452.
17. (a) Correa, A.; Marion, N.; Fensterbank, L.; Malacria, M.; Nolan, S. P.; Cavallo, L. Angew. Chem., Int. Ed. 2008, 47, 718;
b) F(u|¨)rstner, A.; Davies, P. W. Angew. Chem. Int. Ed. 2007, 46, 3410;
c) Marion, N.; Nolan, S. P. Angew. Chem., Int. Ed. 2007, 46, 2750;
d) Marco-Contelles, J.; Soriano, E. Chem. Eur. J. 2007, 13, 1350;
e) Valentin, R. J. Org. Chem. 1984, 49, 950;
f) Mainetti, E.; Mouri(?)s, V.; Dhimane, A.-L.; Fensterbank, V.; Malacria, M. J. Am. Chem. Soc. 2004, 126, 8656;
h) Manane. V.; Gress, T.; Krause, H.; F(u|¨)rstner, A. J. Am. Chem. Soc. 2004, 126, 8654.
18. a) Ji, K.-G.; Shu, X.-Zh.; Chen, J.; Zhao, Sh.-Ch.; Zheng, Zh.-J.; Lu, L.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2008, 10, 3919;
b) Shu, X.-Zh.; Liu, X.-Y.; Ji, K.-G.; Xiao, H.-Q.; Liang, Y.-M. Chem. Eur. J. 2008, 14, 5282;
c) Ji, K.-G.; Shen, Y.-W.; Shu, X.-Zh.; Xiao, H.-Q.; Bian, Y.-J.; Liang, Y.-M. Adv. Synth. Catal. 2008, 350, 1275;
d) Shu, X.-Zh.; Liu, X.-Y.; Xiao, H.-Q.; Ji, K.-G.; Guo, L.-N.; Liang, Y.-M. Adv. Synth. Catal. 2008, 350, 243;
e) Shu, X.-Zh.; Liu, X.-Y.; Xiao, H.-Q.; Ji, K.-G.; Guo, L.-N.; Qi, Ch.-Z.; Liang, Y.-M. Adv. Synth. Catal. 2007, 349, 2493.
19. a) F(u|¨)rstner, A.; Davies, P. W. J. Am. Chem. Soc. 2005, 127, 15024;
b) F(u|¨)rstner, A.; Davies, P. W.; Gress, T. J. Am. Chem. Soc. 2005, 127, 8244;
c) F(u|¨)rstner, A.; Aissa, C. J. Am. Chem. Soc. 2006, 128, 6306;
d) Sohel, S. M. A.; Lin, S.-H.; Liu, R.-S.; Synlett 2008, 5, 745;
e) Das, A.; Liao, H.-H.; Liu, R.-S. J. Org. Chem. 2007, 72, 9214.
20. Li, G.; Zhang, G.; Zhang, L. J. Am. Chem. Soc. 2008, 130, 3740.
21. a) Barluenga, J.; Fernandez-Rodriguez, M. A.; Garcia-Garcia, P.; Aguilar, E. J. Am. Chem. Soc. 2008, 130, 2764;
b) Barluenga, J.; Riesgo, L.; Vicente, R.; Lopez, L. A.; Tomas, M. J. Am. Chem. Soc. 2007, 129, 7772.
22. For select examples on[1,3]-OAt shift, see: a) Zhang, G.; Catalano, V. J.; Zhang, L. J. Am. Chem. Soc. 2007, 129, 11358;
b) Marion, N.; Diez-Gonz(?)lez, S.; Fr(?)mont de, P.; Noble, A. R.; Nolan, S. P. Angew. Chem., Int. Ed 2006, 45, 3647;
c) Zhang, L.; Wang, S. J. Am. Chem. Soc. 2006, 128, 1442;
d) Zhang, L. J. Am. Chem. Soc. 2005, 127, 16804.
23. For examples of aromatization in the air, see: a) Kadzimirsz, D.; Hildebrandt, D.; Merz, K.; Dyker, G. Chem. Commun. 2006, 661;
b) Abbiati, G.; Arcadi, A.; Bianchi, G.; Giuseppe, S. D.; Marinelli, F.; Rossi, E. J. Org. Chem. 2003, 68, 6959;
c)Also see ref(13).