Abstract
Treatment of propargyl alcohol 1 with [Ru]-Cl ([Ru] = CpRu(PPh3)2) in the presence of KPF6 and K2CO3 in CH2Cl2 affords the acetylide complex 2. The dehydration takes place at CδH and CγOH, instead of at CβH and CγOH. Then, protonation of 2 with HBF4 in ether produces the vinylidene complex 3. Formation of 1,3-enyne 5 directly from 1 is catalyzed by 30 mol % of [Ru]NCMe+PF6－ in MeOH at 60oC or indirectly from 3 by stirring the solution in CH3CN/CHCl3 for 12 h. Alkylation of 2 by allyl bromide as an alkylation reagent results in formation of vinylidene complex 4. Intramolecular cyclization of 6a and 6b each containing a hydroxyl group with [Ru]-Cl in the presence of NH4PF6 in CH2Cl2 for 12 h afford oxacyclic carbene complexes 7a and 7b, respectively. However, treatment of 6a and 6b with 10 mol% of [Ru]-Cl in n-BuNH2 at 90oC for 12 h affords the dihydrofuran and dihydropyran products 8a and 8b, respectively.
Epoxidation reaction adds an oxygen atom across the double bond of 5 to yield 1-alkynyloxirane 9. Reaction of 9 with [Ru]-Cl in the presence of KPF6 in MeOH affords the spiro-oxacyclic carbene complex 10. Rearrangement of 9 with a Lewis acid, BF3‧Et2O, affords α-alkynylketone 11 via a ring-expansion process of the cyclopentyl group. Treatment of 11 with [Ru]-Cl in different alcohols in the presence of KPF6 at room temperature affords the fused oxabicyclic carbene complex 12 via intramolecular cyclization reaction. However, in the presence of NH4PF6 in CH2Cl2, the same reaction affords 10 via cascade cyclization/ring-contraction.
When 1,6-enyne 14a is treated with 1 mole equiv. of [Ru]-Cl in the presence of NH4PF6 in CH2Cl2 at room temperature for 24 h, complex 15, the six-membered oxacyclic product 16a, and an aldehyde molecule 17 in a ratio of 1:2:1 are isolated. However, in the presence of KF in MeOH for 12 h, instead of NH4PF6 in CH2Cl2, only 2 is obtained. Three analogous compounds 14b, 14c, and 14d are prepared similarly, using different ketones as staring materials. Furthermore, the reaction of 14a-14d with 20 mol% of [Ru]-Cl in the presence of NH4PF6 in CH2Cl2 at 40oC for 12 h affords six-membered oxacyclic 16a-16d in better yield. In addition, structures of complexes 7a, 10 and 12a’ are confirmed by X-ray diffraction analysis.

Contents I
Numbering and Structure of Compounds II
Reaction Scheme V
Abstract 1
Abstract in Chinese 3
Introduction 4
Results and Discussion 10
Formation of Acetylide Complex 2 10
Protonation and Alkylation of Acetylide Complex 2 12
Formation of 1,3-Enyne Compound 5 13
Formation of the Oxacyclic Carbene Complex 7 15
Formation of the Dihydrofuran and Dihydropyran Derivatives 18
Ring-Opening of Epoxide Compound 9 20
Meinwald Rearrangement Using Lewis Acid 23
Formation of the Fused Oxabicyclic Carbene Complex 12 24
Formation of the Acetylide Complex 13 29
Cyclization Reaction of 1, 6-Enyne 14 31
Conclusions 40
Experimental Section 42
References 66
Appendix I: X-Ray Crystallography Data 72
Appendix II: NMR Spectra Data 98

References
1.(a) Bruce, M. I. Chem. Rev. 1991, 91, 197-257. (b) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311-323. (c) Cadierno, V.; Diex, J.; Gamasa, M. P.; Gimeno, J.; Lastra, E. Coord. Chem. Rev. 1999, 193-195, 147-205.
2.King, R. B.; Saran, M. S. J. Chem. Soc. Chem. Commum. 1972, 1053-1054.
3.(a) de los Rios, I.; Jimenez Tenorio, M.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc. 1997, 119, 6529-6538. (b) Antonova, A. B.; Koloboba, N. E.; Petrovsky, P. V.; Lokshin, B. V.; Obezyuk, N. S. J. Organomet. Chem. 1977, 137, 55-67. (c) Wakatsuki, Y.; Koga, N.; Yamazaki, H.; Morokuma, K. J. Am. Chem. Soc. 1994, 116, 8105-8111. (d) Wakatsuki, Y.; Koga, N.; Werner, H.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 360-366.
4.Gardiene, V.; Gamasa, M. P.; Gimeno, J. Eur. J. Inorg. Chem. 2001, 571.
5.Winter, R. F.; Zali&;#353;, S. Coord. Chem. Rev. 2004, 248, 1565-1583.
6.(a) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Gonazalez-Cueva, M.; Lastra, E.; Borge, J.; Garcia-Granada, S.; Perex-Carrrno, E. Organometallics 1996, 15, 2137-2147. (b) Esteruelas, M. A.; Gomez, A. V.; Lopez, A. M.; Modrego, J.; Onate, E. Organometallics 1997, 16, 5826-5835. (c) Auger, N.; Touchard, D.; Rigaut, S.; Halet, J.; Saillard, J. Organometallics 2003, 22, 1638-1644.
7.Selegue, J. P. Organometallics 1982, 1, 217-218.
8.(a) Castarlenas, R.; Esteruelas, M. A.; Lalrempuia, R.; Olivan, M.; Onate, E. Organometallics 2008, 27, 795-798. (b) Ojo, W. S.; Petillon, F. Y.; Schollhammer, P.; Talarmin, J.; Muir, K. W. Organometallics 2006, 25, 5503-5505. (c) Szesni, N.; Drexler, M.; Maurer, J.; Winter, R. F.; Montigny, F.; Lapinte, C.; Steffens, S.; Heck, J.; Weibert, B.; Fisher, H. Organometallics 2006, 25, 5774-5787.
9.(a) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Lastra, E.; Borge, J.; Garcia-Granda, S. Organometallics 1994, 13, 745-747. (b) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Borge, J.; Garcia-Granda, S. Organometallics 1997, 16, 3178-3187.
10.(a) Tanaka, M.; Ubukata, M.; Matsuo, T.; Yasue, K.; Matsumoto, K.; Kajimoto, Y.; Ogo, T.; Inaba, T. Org. Lett. 2007, 9, 3331-3334. (b) Tsuritani, T.; Yamamoto, Y.; Kawasaki, M.; Mase, T. Org. Lett. 2009, 11, 1043-1045. (c) Trost, B. M.; Xie, J.; Maulide, N. J. Am. Chem. Soc. 2008, 130, 17258-17259.
11.(a) Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117-179. (b) Zuo, G.; Louie, J. Angew. Chem. 2004, 116, 2327-2329; Angew. Chem. Int. Ed. 2004, 43, 2277-2279. (c) Brandi, A.; Cicchi, S.; Cordero, F. M.; Goti, A. Chem. Rev. 2003, 103, 1213-1269. (d) Terao, J.; Tomita, M.; Singh, S. P.; Kambe, N. Angew. Chem. 2010, 122, 148-151; Angew. Chem. Int. Ed. 2010, 49, 144-147.
12.(a) Suzuki, T.; Fujimoto, H. Inorg. Chem. 2000, 39, 1113-1119. (b) Creary, X.; Losch, A.; Sullivan, W. J. Org. Chem. 2007, 72, 7930-7938. (c) Itazaki, M.; Nishihara, Y.; Osakada, K. J. Org. Chem. 2002, 67, 6889-6895.
13.(a) Gustavson, G. J. Prakt. Chem. 1896, 54, 104-107. (b) Vinogradov, M. G.; Zinenkov, A. Z. Russ. Chem. Rev 1996, 65, 131-145.
14.(a) Liu, L.-P.; Lu, J.-M.; Shi ,M. Org. Lett. 2007, 9, 1303-1306. (b) Baldwin, J. E.; Shukla, R. Org. Lett. 1999, 1, 1081-1082.
15.(a) Jiang, M.; Shi, M. Org. Lett. 2008, 10, 2239-2242. (b) Liang, Y.; Jiao, L.; Wang, Y.-Y.; Chen, Y.-Y.; Ma, L.; Xu, J.; Zhang, S.; Yu, Z.-X. Org. Lett. 2006, 8, 5877-5879. (c) Shen, Y.-M.; Wang, B.; Shi, Y. Angew. Chem. 2006, 118, 1457-1460; Angew. Chem. Int. Ed. 2006, 45, 1429-1432.
16.Rossi, R.; Diversi, P.; Porri, L. Macromolecules 1972, 5, 662.
17.Chen, C.-C.; Cheng, P.-C.; Huang, S.-L.; Lin, Y.-C.; Liu, Y.-H. Chem. Asian J. 2011, 6, 3122-3131.
18.Wang, Y.-C.; Lin, Y.-C.; Liu, Y.-H. Chem. Asian J. 2012, 7, 2703-2710.
19.(a) Gonzalez, M. J.; Gonzalez J.; Perez-Calleja, C.; Lopez, L. A.; Vicente, R. Catal. Sci. Technol. 2013, 3, 932-934. (b) Robinson, M. W. C.; Davies, A. M.; Buckle, R.; Mabbett, I.; Taylor, S. H.; Graham, A. E. Org. Biomol. Chem. 2009, 7, 2559-2564. (c) Szostak, M.; Aube, J. J. Am. Chem. Soc., 2009, 131, 13246-13247. (d) Lewis, J. B.; Hedrick, G. W. J. Org. Chem. 1965, 30, 4271-4275. (e) Kita, Y.; Futamura, J.; Ohba,Y.; Sawama, Y.; Ganesh, J. K.; Fujioka, H. J. J. Org. Chem. 2003, 68, 5917-5924. (f) Donald, J. R.; Taylor, R. J. K. Synlett. 2009, 1, 59-62.
20.Hashmi, A. S. K.; Sinha, P. Adv. Synth. Catal. 2004, 346, 432-438.
21.(a) Yoshida, M.; Al-Amin, M.; Matsuda, K.; Shishido, K. Tetrahedron Lett. 2008, 49, 5021-5023. (b) Yoshida, M.; Al-Amin, M.; Shishido, K. Synthesis 2009, 2454-2466.
22.(a) Blanc, A.; Tenbrink, K.; Weibel, J.-M.; Pale, P. J. Org. Chem. 2009, 74, 4360-4363. (b) Blanc, A.; Tenbrink, K.; Weibel, J.-M.; Pale, P. J. Org. Chem. 2009, 74, 5342-5348. (c) Blanc, A.; Alix, A.; Weibel, J.-M.; Pale, P. Eur. J. Org. Chem. 2010, 1644-1647.
23.Kang, J. Y.; Connell, B. T. J. Org. Chem. 2011, 76, 2379-2383.
24.(a) Maulide, N.; Marko, I. E. Org. Lett. 2006, 8, 3705-3707. (b) Paquette, L. A.; Owen, D. R.; Bibart, R. T.; Seekamp, C. K.; Kahane, A. L.; Lanter, J. C.; Corral, M. A. J. Org. Chem. 2001, 66, 2828-2834. (c) Michaut, M.; Santelli, M.; Parrain, J.-L. J. Organomet. Chem. 2000, 606, 93-96.
25.(a) Gulias, M.; Rodriguez, J. R.; Castedo, L.; Mascarenas J. L. Org. Lett. 2003, 5, 1976-1977. (b) Yakura, T.; Yamada, S.; Shima, M.; Iwamoto, M.; Ikeda, M. Chem. Pharm. Bull. 1998, 46, 744-748.
26.(a) Schmidta, B.; Nave, S. Adv. Synth. Catal. 2007, 349, 215-230. (b) Mack, D. J.; Batory, L. A.; Njardarson, J. T. Org. Lett. 2012, 14, 378-381. (c) Nicolai, S.; Waser, J. Org. Lett. 2011, 13, 6324-6327. (d) Nicolai, S.; Waser, J. Org. Lett. 2011, 13, 6324-6327.
27.(a) Davies, H. G.; Green, R. H. Nat. Prod. Rep. 1986, 3, 87-121. (b) Davies, H. G.; Green, R. H. Chem. Soc. Rev. 1991, 20, 211; 271.
28.Navarro, E.; Alanso, S. J.; Trujillo, J.; Jorge, E.; Perez, C. J. Nat. Prod. 2001, 64, 134-135.
29.Silva, D. H. S.; Pereira, F. C.; Zanoni, M. V. B.; Yoshida, M. Phytochemistry 2001, 57, 437-442.
30.Mortensen, D. S.; Rodriguez, A. L.; Carlson, K. E.; Sun, J.; Katzenellenbogen, B. S.; Katzenellenbogen, J. A. J. Med. Chem. 2001, 44, 3838-3848.
31.(a) Yen, Y.-S.; Lin, Y.-C.; Liu, Y.-H.; Wang, Y. Organometallics 2007, 26, 1250-1255. (b) Borguet, Y.; Sauvage, X.; Zaragoza, G.; Demonceau, A.; Delaude, L. Organometallics 2011, 30, 2730-2738.
32.(a) Ipaktschi, J.; Mirzaei, F.; Reimann, K.; Beck, J.; Serafin, M. Organometallics 1998, 17, 5086-5090. (b) Yen, Y.-S.; Lin, Y.-C.; Huang, S.-L.; Liu, Y.-H.; Sung, H.-L.; Wang, Y. J. Am. Chem. Soc. 2005, 127, 18037-18045.
33.(a) Cadierno, V.; Conejero, S.; Gamasa, M. P.; Gimeno, J. Organometallics 2002, 21, 3837-3840. (b) Cadierno, V.; Gamasa, M. P.; Gimeno, J. Organometallics 2009, 18, 2821-2832.
34.Cabezas, J. A.; Pereira, A. R.; Amey, A. Tetrahedron Lett. 2001, 42, 6819-6822.
35.Varela-Fernandez, A.; Gonzalez-Rodriguez, C.; Varela, J. A.; Castedo, L.; Saa, C. Org. Lett. 2009, 11, 5350-5353.
36.(a) McDonald, F. E.; Connolly, C. B.; Gleason, M. M.; Towne, T. B.; Treiber, K. D. J. Org. Chem. 1993, 58, 6952-6953. (b) McDonald, F. E.; Schultz, C. C. J. Am. Chem. Soc. 1994, 116, 9363-9364. (c) McDonald, F. E.; Bowman, J. L. Tetrahedron Lett. 1996, 37, 4675-4678. (d) McDonald, F. E.; Gleason, M. M. J. Am. Chem. Soc. 1996, 118, 6648-6659. (e) McDonald, F. E.; Zhu, H. Y. H. Tetrahedron 1997, 53, 11061-11068. (f) McDonald, F. E.; Zhu, H. Y. H. J. Am. Chem. Soc. 1998, 120, 4246-4247. (g) McDonald, F. E.; Reddy, K. S.; Diaz, Y. J. Am. Chem. Soc. 2000, 122, 4304-4309.
37.(a) Halazy, S.; Zutterman, F.; Kries, A. Tetrahedron Lett. 1982, 23, 4385-4388. (b) Trofimov, A.; Chernyak, N.; Gevorgyan, V. J. Am.Chem. Soc. 2008, 130, 13538-13539. (c) Tobe, Y.; Yamashita, T.; Kakiuchi, K.; Odaira, Y. J. Chem. Soc. Chem. Commun. 1985, 898-899. (d) Michele, L.; Antonio, G.; Francesco, P. J. Org. Chem. 1980, 45, 1704-1705.
38.Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry. Sausalito, CA: University Science, 2006. 100-109.
39.Chang, W.-C.; Cheng, C.-W.; Ma, H.-W.; Lin, Y.-C.; Liu, Y.-H. Organometallics 2011, 30, 2747-2754.
40.(a) Dubovyk, I.; Pichugin, D.; Yudin, A. K. Angew. Chem. Int. Ed. 2011, 50, 5924-5926. (b) Silva, L. F. Jr. Tetrahedron 2002, 9137-9161.
41.(a) Hyder, I.; Jimenez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 2011, 30, 726-737. (b) Oppolzer, W.; Snieckus, V. Angew. Chem. Int. Ed. Engl. 1978, 17, 476-486. (c) Dubac, J.; Laporterie, A. Chem. Rev. 1987, 87, 319-334.
42.(a) Zhang, L.-L.; Zhang, W.-Z.; Ren, X.; Tan, X.-Y.; Lu, X.-B. Tetrahedron Letters 2012, 53, 3389-3392. (b) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317-1382. (c) Hansen, E. C.; Lee, D. Acc. Chem. Res. 2006, 39, 509-519. (d) Mori, M. Adv. Synth. Catal. 2007, 349, 121-135. (e) Diver, S. T. Coord. Chem. Rev. 2007, 251, 671-701.
43.(a) Maifeld, S. V.; Lee, D. Chem. Eur. J. 2005, 11, 6118-6126. (b) Villar, H.; Frings, M.; Bolm, C. Chem. Soc. Rev. 2007, 36, 55-66. (c) Majumdar, K. C. RSC Adv. 2011, 1, 1152-1170.
44.(a) Kinoshita, A.; Mori, M. Synlett 1994, 1020-1022. (b) Kim, S.-H.; Zuercher, W. J.; Bowden, N. B.; Grubbs, R. H. J. Org. Chem. 1996, 61, 1073-1081. (c) Furstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236-3253. (d) Kitamura, T.; Sato, Y.; Mori, M. Adv. Synth. Catal. 2002, 344, 678-693. (e) Guo, H.; Madhushaw, R. J.; Shen, F.-M.; Liu, R.-S. Tetrahedron 2002, 58, 5627-5637. (f) Castarlenas, R.; Eckert, M.; Dixneuf, P. H. Angew. Chem. Int. Ed. 2005, 44, 2576-2579. (g) Kim, B. G.; Snapper, M. L. J. Am. Chem. Soc. 2006, 128, 52-53.
45.Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471-1485.
46.Ashby, G. S.; Bruce, M. I.; Tomkins, I. B.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1003-1016.