C-C-Bond Formation by the Palladium-Catalyzed Cycloisomerization/Dimerization of Terminal Allenyl Ketones: Selectivity and Mechanistic Aspects

Journal of Organic Chemistry

Volumn 62, Issue 21, 1997, Pages 7295-7304

  Hashmi, A Stephen K ^a,b   Ruppert, Thorsten L ^a   Knöfel, Thomas ^a   Bats, Jan W ^a  

^a FREIE UNIVERSITÄT BERLIN   (Germany)

^b GOETHE UNIVERSITY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000706688     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970837l     Document Type: Article

References (197)

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61. 13C NMR spectra, would be a α-alkylidene pyran formed by Diels-Alder reaction and subsequent double bond migration: Chemical equation presents For a related [4 + X] reaction of carbon monoxide (X = 1) instead of an allenic double bond (X = 2), see: Sigman, M. S.; Kerr, C. E.; Eaton, B. E. J. Am. Chem. Soc. 1993, 115, 7545-7546. Sigman, M. S.; Eaton, B. E.; Heise, J. D. Kubiak, C. P. Organometallics 1996, 15, 2829-2832. But NOE-data and UV-spectra do not agree with this structure, too.
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71. 75 Chemical equation presents For such additions of carboxylic acids to allenes, see: Smadja, W. Chem. Rev. 1983, 83, 263-320. Pasto, D. J. Tetrahedron 1984, 40, 2805-2827.
72. 75 Chemical equations presents For such additions of carboxylic acids to allenes, see: Smadja, W. Chem. Rev. 1983, 83, 263-320. Pasto, D. J. Tetrahedron 1984, 40, 2805-2827.
73. 75 Chemical equation presents For such additions of carboxylic acids to allenes, see: Smadja, W. Chem. Rev. 1983, 83, 263-320. Pasto, D. J. Tetrahedron 1984, 40, 2805-2827.
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109. 2, see: Pearlman, B. A.; McNamara, J. M.; Hasan, I.; Hatakeyama, S.; Sekizaki, H.; Kishi, Y. J. Am. Chem. Soc. 1981, 103, 4248-4251. Hosokawa, T. Nakajima, F.; Iwasa, S.; Murahashi, S.-I. Chem. Lett. 1990, 1387-1390. Kumar, R. J.; Krupadanam, G. L. D.; Srimannarayana, G. Synthesis 1990, 535-538. Saito, S.; Hara, T.; Takahashi, N.; Hirai, M.; Moriwake, T. Synlett 1992, 237-238.
110. Reviews: (a) Canty, A. J. Acc. Chem. Res. 1992, 25, 83-90. (b) Canty, A. J. Platinum Metals Rev. 1993, 37, 2-7. (c) Canty, A. J., ref 42c, vol. 9, pp 225-290 (specific pp 272-276).
111. Reviews: (a) Canty, A. J. Acc. Chem. Res. 1992, 25, 83-90. (b) Canty, A. J. Platinum Metals Rev. 1993, 37, 2-7. (c) Canty, A. J., ref 42c, vol. 9, pp 225-290 (specific pp 272-276).
112. Reviews: (a) Canty, A. J. Acc. Chem. Res. 1992, 25, 83-90. (b) Canty, A. J. Platinum Metals Rev. 1993, 37, 2-7. (c) Canty, A. J., ref 42c, vol. 9, pp 225-290 (specific pp 272-276).
113. For more recent work, see: (d) Canty, A. J.; Jin, H.; Roberts, A. S.; Skelton, B. W.; White, A. H. Organometallics 1996, 15, 5713-5722.
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118. Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1985, 107, 1781-1783. Trost, B. M.; Chung, J. Y. L. J. Am. Chem. Soc. 1985, 107, 4586-4588. Canty, A. J.; van Koten, G. Acc. Chem. Res. 1995, 28, 406-413. Shimada, S.; Tanaka, M.; Shiro, M. Angew. Chem. 1996, 108, 1970-1972; Angew. Chem., Int. Ed. Engl. 1996, 35, 1856-1858. Grushin, V. V. Chem. Rev. 1996, 96, 2011-2033.
119. Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1985, 107, 1781-1783. Trost, B. M.; Chung, J. Y. L. J. Am. Chem. Soc. 1985, 107, 4586-4588. Canty, A. J.; van Koten, G. Acc. Chem. Res. 1995, 28, 406-413. Shimada, S.; Tanaka, M.; Shiro, M. Angew. Chem. 1996, 108, 1970-1972; Angew. Chem., Int. Ed. Engl. 1996, 35, 1856-1858. Grushin, V. V. Chem. Rev. 1996, 96, 2011-2033.
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123. Ebsworth, E. A. V.; Marganian, V. M.; Reed, F. J. S.; Gould, R. O. J. Chem. Soc., Dalton Trans. 1978, 1167-1170. Arnold, D. P.; Bennett, M. A. Inorg. Chem. 1984, 23, 2110-2116. Wehman-Ooyevaar, I. C. M.; Grove, D. M.; de Vaal, P.; Dedieu, A.; van Koten, G. Inorg. Chem. 1992, 31, 5484-5493. De Felice, V.; de Renzi, A.; Panunzi, A.; Tesauro, D. J. Organomet. Chem. 1995, 488, C13-C14. Hill, G. S.; Puddephatt, R. J. J. Am. Chem. Soc. 1996, 118, 8745-8746. Canty, A. J.; Dedieu, A.; Jin, H.; Milet, A.; Richmond, M. K. Organometallics 1996, 15, 2845-2847. Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848-849.
124. Ebsworth, E. A. V.; Marganian, V. M.; Reed, F. J. S.; Gould, R. O. J. Chem. Soc., Dalton Trans. 1978, 1167-1170. Arnold, D. P.; Bennett, M. A. Inorg. Chem. 1984, 23, 2110-2116. Wehman-Ooyevaar, I. C. M.; Grove, D. M.; de Vaal, P.; Dedieu, A.; van Koten, G. Inorg. Chem. 1992, 31, 5484-5493. De Felice, V.; de Renzi, A.; Panunzi, A.; Tesauro, D. J. Organomet. Chem. 1995, 488, C13-C14. Hill, G. S.; Puddephatt, R. J. J. Am. Chem. Soc. 1996, 118, 8745-8746. Canty, A. J.; Dedieu, A.; Jin, H.; Milet, A.; Richmond, M. K. Organometallics 1996, 15, 2845-2847. Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848-849.
125. Ebsworth, E. A. V.; Marganian, V. M.; Reed, F. J. S.; Gould, R. O. J. Chem. Soc., Dalton Trans. 1978, 1167-1170. Arnold, D. P.; Bennett, M. A. Inorg. Chem. 1984, 23, 2110-2116. Wehman-Ooyevaar, I. C. M.; Grove, D. M.; de Vaal, P.; Dedieu, A.; van Koten, G. Inorg. Chem. 1992, 31, 5484-5493. De Felice, V.; de Renzi, A.; Panunzi, A.; Tesauro, D. J. Organomet. Chem. 1995, 488, C13-C14. Hill, G. S.; Puddephatt, R. J. J. Am. Chem. Soc. 1996, 118, 8745-8746. Canty, A. J.; Dedieu, A.; Jin, H.; Milet, A.; Richmond, M. K. Organometallics 1996, 15, 2845-2847. Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848-849.
126. Ebsworth, E. A. V.; Marganian, V. M.; Reed, F. J. S.; Gould, R. O. J. Chem. Soc., Dalton Trans. 1978, 1167-1170. Arnold, D. P.; Bennett, M. A. Inorg. Chem. 1984, 23, 2110-2116. Wehman-Ooyevaar, I. C. M.; Grove, D. M.; de Vaal, P.; Dedieu, A.; van Koten, G. Inorg. Chem. 1992, 31, 5484-5493. De Felice, V.; de Renzi, A.; Panunzi, A.; Tesauro, D. J. Organomet. Chem. 1995, 488, C13-C14. Hill, G. S.; Puddephatt, R. J. J. Am. Chem. Soc. 1996, 118, 8745-8746. Canty, A. J.; Dedieu, A.; Jin, H.; Milet, A.; Richmond, M. K. Organometallics 1996, 15, 2845-2847. Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848-849.
127. O'Reilly, S. A.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 1996, 118, 5684-5689.
128. MeCN is considered to be a good σ-donor and a weak π-acceptor, but still to be labile enough to be substituted by the substrate: Storhoff, B. N.; Lewis, H. C., Jr. Coord. Chem. Rev. 1977, 23, 1-29.
129. Endres, H. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: Oxford, 1987; vo1. 2, pp 261-267.
130. Cherniak, E. A.; Costain, C. C. J. Chem. Phys. 1966, 45, 104-110. Montaudo, G.; Librando, V.; Caccamese, S.; Maravinga, P. J. Am. Chem. Soc. 1973, 95, 6365-6370. Bienvenüe, A. J. Am. Chem. Soc. 1973, 95, 7345-7353.
131. Cherniak, E. A.; Costain, C. C. J. Chem. Phys. 1966, 45, 104-110. Montaudo, G.; Librando, V.; Caccamese, S.; Maravinga, P. J. Am. Chem. Soc. 1973, 95, 6365-6370. Bienvenüe, A. J. Am. Chem. Soc. 1973, 95, 7345-7353.
132. Cherniak, E. A.; Costain, C. C. J. Chem. Phys. 1966, 45, 104-110. Montaudo, G.; Librando, V.; Caccamese, S.; Maravinga, P. J. Am. Chem. Soc. 1973, 95, 6365-6370. Bienvenüe, A. J. Am. Chem. Soc. 1973, 95, 7345-7353.
133. So far X-ray structure analyses of only six allenyl ketones are described in the CCDB; due to geometrical restrictions like rings none of them provided a reliable value for the C-O-distance.
134. For the only X-ray structure of a Pd-allene complex, see: Okamoto, K.; Kai, Y.; Yasuoka, N.; Kasai, N. J. Organomet. Chem. 1974, 65, 427-441. For the only two late transition-metal complexes of allenyl ketones, see: Suades, J.; Dahan, F.; Mathieu, R. Organometallics 1988, 7, 47-51. Casey, C. P.; Underiner, T. L.; Vosejpka, P. C.; Gavney, J. A., Jr.; Kiprof, P. J. Am. Chem. Soc. 1992, 114, 10826-10834.
135. For the only X-ray structure of a Pd-allene complex, see: Okamoto, K.; Kai, Y.; Yasuoka, N.; Kasai, N. J. Organomet. Chem. 1974, 65, 427-441. For the only two late transition-metal complexes of allenyl ketones, see: Suades, J.; Dahan, F.; Mathieu, R. Organometallics 1988, 7, 47-51. Casey, C. P.; Underiner, T. L.; Vosejpka, P. C.; Gavney, J. A., Jr.; Kiprof, P. J. Am. Chem. Soc. 1992, 114, 10826-10834.
136. For the only X-ray structure of a Pd-allene complex, see: Okamoto, K.; Kai, Y.; Yasuoka, N.; Kasai, N. J. Organomet. Chem. 1974, 65, 427-441. For the only two late transition-metal complexes of allenyl ketones, see: Suades, J.; Dahan, F.; Mathieu, R. Organometallics 1988, 7, 47-51. Casey, C. P.; Underiner, T. L.; Vosejpka, P. C.; Gavney, J. A., Jr.; Kiprof, P. J. Am. Chem. Soc. 1992, 114, 10826-10834.
137. For the participation of carbonyl-oxygen in oxypalladation steps, see: Imi, K.; Imai, K.; Utimoto, K. Tetrahedron Lett. 1987, 28, 3127-3130.
138. Pd(0): (a) Busacca, C. A.; Swestock, J.; Johnson, R. E.; Bailey, T. R.; Musza, L.; Rodger, C. A. J. Org. Chem. 1994, 59, 7553-7556. (b) Monteiro, N.; Goré, J; van Hemelryck, B.; Balme, G. Synlett 1994, 447-449. (c) Farina, V.; Hossain, M. A. Tetrahedron Lett. 1996, 37, 6997-7000.
139. Pd(0): (a) Busacca, C. A.; Swestock, J.; Johnson, R. E.; Bailey, T. R.; Musza, L.; Rodger, C. A. J. Org. Chem. 1994, 59, 7553-7556. (b) Monteiro, N.; Goré, J; van Hemelryck, B.; Balme, G. Synlett 1994, 447-449. (c) Farina, V.; Hossain, M. A. Tetrahedron Lett. 1996, 37, 6997-7000.
140. Pd(0): (a) Busacca, C. A.; Swestock, J.; Johnson, R. E.; Bailey, T. R.; Musza, L.; Rodger, C. A. J. Org. Chem. 1994, 59, 7553-7556. (b) Monteiro, N.; Goré, J; van Hemelryck, B.; Balme, G. Synlett 1994, 447-449. (c) Farina, V.; Hossain, M. A. Tetrahedron Lett. 1996, 37, 6997-7000.
141. Pd(II): (d) Dixon, K. R.; Dixon, A. C., ref 42c, vol. 9, pp 193-223 (specific pp 216-220). (e) Maitlis, P. M.; Espinet, P.; Russell, M. J. H. in ref 1b, vol. 6, pp 279-349 (specific pp 292-296). (f) Trost, B. M.; Hashmi, A. S. K. Angew. Chem. 1993, 105, 1130-1132; Angew. Chem., Int. Ed. Engl. 1993, 32, 1085-1087. (g) Trost, B. M.; Hashmi, A. S. K. J. Am. Chem. Soc. 1994, 116, 2183-2184.
142. Pd(II): (d) Dixon, K. R.; Dixon, A. C., ref 42c, vol. 9, pp 193-223 (specific pp 216-220). (e) Maitlis, P. M.; Espinet, P.; Russell, M. J. H. in ref 1b, vol. 6, pp 279-349 (specific pp 292-296). (f) Trost, B. M.; Hashmi, A. S. K. Angew. Chem. 1993, 105, 1130-1132; Angew. Chem., Int. Ed. Engl. 1993, 32, 1085-1087. (g) Trost, B. M.; Hashmi, A. S. K. J. Am. Chem. Soc. 1994, 116, 2183-2184.
143. Pd(II): (d) Dixon, K. R.; Dixon, A. C., ref 42c, vol. 9, pp 193-223 (specific pp 216-220). (e) Maitlis, P. M.; Espinet, P.; Russell, M. J. H. in ref 1b, vol. 6, pp 279-349 (specific pp 292-296). (f) Trost, B. M.; Hashmi, A. S. K. Angew. Chem. 1993, 105, 1130-1132; Angew. Chem., Int. Ed. Engl. 1993, 32, 1085-1087. (g) Trost, B. M.; Hashmi, A. S. K. J. Am. Chem. Soc. 1994, 116, 2183-2184.
144. Pd(II): (d) Dixon, K. R.; Dixon, A. C., ref 42c, vol. 9, pp 193-223 (specific pp 216-220). (e) Maitlis, P. M.; Espinet, P.; Russell, M. J. H. in ref 1b, vol. 6, pp 279-349 (specific pp 292-296). (f) Trost, B. M.; Hashmi, A. S. K. Angew. Chem. 1993, 105, 1130-1132; Angew. Chem., Int. Ed. Engl. 1993, 32, 1085-1087. (g) Trost, B. M.; Hashmi, A. S. K. J. Am. Chem. Soc. 1994, 116, 2183-2184.
145. Pd(II): (d) Dixon, K. R.; Dixon, A. C., ref 42c, vol. 9, pp 193-223 (specific pp 216-220). (e) Maitlis, P. M.; Espinet, P.; Russell, M. J. H. in ref 1b, vol. 6, pp 279-349 (specific pp 292-296). (f) Trost, B. M.; Hashmi, A. S. K. Angew. Chem. 1993, 105, 1130-1132; Angew. Chem., Int. Ed. Engl. 1993, 32, 1085-1087. (g) Trost, B. M.; Hashmi, A. S. K. J. Am. Chem. Soc. 1994, 116, 2183-2184.
146. See also ref 54. For stable bis-carbene complexes of Pd(II), see: (h) Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. J. Angew. Chem. 1995, 107, 2602-2605; Angew. Chem., Int. Ed. Engl. 1995, 34, 2371-2374. (i) Enders, D.; Gielen, H.; Raabe, G.; Runsink, J.; Teles, J. H. Chem. Ber. 1996, 129, 1483-1488.
147. See also ref 54. For stable bis-carbene complexes of Pd(II), see: (h) Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. J. Angew. Chem. 1995, 107, 2602-2605; Angew. Chem., Int. Ed. Engl. 1995, 34, 2371-2374. (i) Enders, D.; Gielen, H.; Raabe, G.; Runsink, J.; Teles, J. H. Chem. Ber. 1996, 129, 1483-1488.
148. See also ref 54. For stable bis-carbene complexes of Pd(II), see: (h) Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. J. Angew. Chem. 1995, 107, 2602-2605; Angew. Chem., Int. Ed. Engl. 1995, 34, 2371-2374. (i) Enders, D.; Gielen, H.; Raabe, G.; Runsink, J.; Teles, J. H. Chem. Ber. 1996, 129, 1483-1488.
149. (a) Wada, M.; Koyama,Y. J. Organomet. Chem. 1980, 201, 477-491.
150. (b) Wada, M.; Koyama, Y.; Sameshima, K. J. Organomet. Chem. 1981, 209, 115-121.
151. The protonation of furans occurs in 2-position: Unverferth, K.; Schwetlick, K. J. Prakt. Chem. 1970, 312, 882-886. Salomaa, P.; Kankaanperä, A.; Nikander, E.; Kaipainen, K.; Aaltonen, R. Acta Chem. Scand. 1973, 27, 153-163.
152. The protonation of furans occurs in 2-position: Unverferth, K.; Schwetlick, K. J. Prakt. Chem. 1970, 312, 882-886. Salomaa, P.; Kankaanperä, A.; Nikander, E.; Kaipainen, K.; Aaltonen, R. Acta Chem. Scand. 1973, 27, 153-163.
153. For the agostic interaction of hydrogen in a Pd(II) complex, see: Roe, D. M.; Bailey, P. M.; Moseley, K.; Maitlis, P. M. J. Chem. Soc., Chem. Commun. 1972, 1273-1274. Compare also Ryabov, A. D. Chem. Rev. 1990, 90, 403-424.
154. For the agostic interaction of hydrogen in a Pd(II) complex, see: Roe, D. M.; Bailey, P. M.; Moseley, K.; Maitlis, P. M. J. Chem. Soc., Chem. Commun. 1972, 1273-1274. Compare also Ryabov, A. D. Chem. Rev. 1990, 90, 403-424.
155. The (partially) reverse reaction, the formation of a carbene complex by the protonation of a vinyl complex has been described for Pd (ref 54a) and Ni, see: Wada, M.; Sameshima, K.; Nishiwaki, K.; Kawasaki, Y. J. Chem. Soc., Dalton Trans. 1982, 793-797.
156. (a) Fournier-Nguefack, C.; Lhoste, P.; Sinou, D. Synlett 1996, 553-554.
157. (b) Yamamoto, A. J. Organomet. Chem. 1995, 500, 337-348.
158. 3-allylpalladium(II) complexes, see ref 37. With Ni(II)-compounds, see: (c) Pasynkiewicz, S. J. Organomet. Chem. 1995, 500, 283-288.
159. Müller, P.; Pautex, N.; Doyle, M. P.; Bagheri, V. Helv. Chim. Acta 1990, 73, 1233-1241. Taber, D. F.; Hennessy, M. J.; Louey, J. P. J. Org. Chem. 1992, 57, 436-441 and literature cited therein. Compare: Taber, D. F. In Houben Weyl; Helmchen, G., Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.; Thieme: Stuttgart, 1995; vol. E21a, pp 1127-1148 (specific p 1145).
160. Müller, P.; Pautex, N.; Doyle, M. P.; Bagheri, V. Helv. Chim. Acta 1990, 73, 1233-1241. Taber, D. F.; Hennessy, M. J.; Louey, J. P. J. Org. Chem. 1992, 57, 436-441 and literature cited therein. Compare: Taber, D. F. In Houben Weyl; Helmchen, G., Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.; Thieme: Stuttgart, 1995; vol. E21a, pp 1127-1148 (specific p 1145).
161. Müller, P.; Pautex, N.; Doyle, M. P.; Bagheri, V. Helv. Chim. Acta 1990, 73, 1233-1241. Taber, D. F.; Hennessy, M. J.; Louey, J. P. J. Org. Chem. 1992, 57, 436-441 and literature cited therein. Compare: Taber, D. F. In Houben Weyl; Helmchen, G., Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.; Thieme: Stuttgart, 1995; vol. E21a, pp 1127-1148 (specific p 1145).
162. Shirafuji, T.; Yamamoto, Y.; Nozaki, H. Tetrahedron Lett. 1971, 4713-4714. Leftin, J. H.; Gil-Av, E. Tetrahedron Lett. 1972, 3367-3370.
163. Shirafuji, T.; Yamamoto, Y.; Nozaki, H. Tetrahedron Lett. 1971, 4713-4714. Leftin, J. H.; Gil-Av, E. Tetrahedron Lett. 1972, 3367-3370.
164. Such β-H-eliminations usually follow the oxypalladation of olefins, see ref 43.
165. Yamamoto, Y.; Al-Masum, M.; Asao, N. J. Am. Chem. Soc. 1994, 116, 6019-6020. Carbopalladation of a acceptorsubstituted alkene by a Pd(II)-H species was suggested by Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1996, 118, 6305-6306.
166. Yamamoto, Y.; Al-Masum, M.; Asao, N. J. Am. Chem. Soc. 1994, 116, 6019-6020. Carbopalladation of a acceptorsubstituted alkene by a Pd(II)-H species was suggested by Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1996, 118, 6305-6306.
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169. Shimizu, I.; Tsuji, J. Chem. Lett. 1984, 233-236. Larock, R. C.; Varaprath, S.; Lau, H. H.; Fellows, C. A. J. Am. Chem. Soc. 1984, 106, 5274-5284. Larock, R. C.; Berrios-Pena, N. G.; Fried, C. A. J. Org. Chem. 1991, 56, 2615-2617. Davies, I. W.; Scopes, D. I. C.; Gallagher, T. Synlett 1993, 85-87.
170. Shimizu, I.; Tsuji, J. Chem. Lett. 1984, 233-236. Larock, R. C.; Varaprath, S.; Lau, H. H.; Fellows, C. A. J. Am. Chem. Soc. 1984, 106, 5274-5284. Larock, R. C.; Berrios-Pena, N. G.; Fried, C. A. J. Org. Chem. 1991, 56, 2615-2617. Davies, I. W.; Scopes, D. I. C.; Gallagher, T. Synlett 1993, 85-87.
171. Pasto, D. J.; Huang, N.-Z.; Eigenbrot, C. W. J. Am. Chem. Soc. 1985, 107, 3160-3172. Hegedus, L. S.; Kambe, N.; Ishii, Y.; Mori, A. J. Org. Chem. 1985, 50, 2240-2243. Stephan, C.; Munz, C.; tom Dieck, H. J. Organomet. Chem. 1994, 468, 273-278. Hughes, R. P.; Powell, J. J. Organomet. Chem. 1969, 20, P17-P19. Broadbent, T. A.; Pringle, G. E. J. Inorg. Nucl. Chem. 1971, 33, 2009-2014. For related palladacycles in the formal oxidation state (IV), see ref 35 and Blomquist, A. T.; Maitlis, P. M. J. Am. Chem. Soc. 1962, 84, 2329-2334.
172. Pasto, D. J.; Huang, N.-Z.; Eigenbrot, C. W. J. Am. Chem. Soc. 1985, 107, 3160-3172. Hegedus, L. S.; Kambe, N.; Ishii, Y.; Mori, A. J. Org. Chem. 1985, 50, 2240-2243. Stephan, C.; Munz, C.; tom Dieck, H. J. Organomet. Chem. 1994, 468, 273-278. Hughes, R. P.; Powell, J. J. Organomet. Chem. 1969, 20, P17-P19. Broadbent, T. A.; Pringle, G. E. J. Inorg. Nucl. Chem. 1971, 33, 2009-2014. For related palladacycles in the formal oxidation state (IV), see ref 35 and Blomquist, A. T.; Maitlis, P. M. J. Am. Chem. Soc. 1962, 84, 2329-2334.
173. Pasto, D. J.; Huang, N.-Z.; Eigenbrot, C. W. J. Am. Chem. Soc. 1985, 107, 3160-3172. Hegedus, L. S.; Kambe, N.; Ishii, Y.; Mori, A. J. Org. Chem. 1985, 50, 2240-2243. Stephan, C.; Munz, C.; tom Dieck, H. J. Organomet. Chem. 1994, 468, 273-278. Hughes, R. P.; Powell, J. J. Organomet. Chem. 1969, 20, P17-P19. Broadbent, T. A.; Pringle, G. E. J. Inorg. Nucl. Chem. 1971, 33, 2009-2014. For related palladacycles in the formal oxidation state (IV), see ref 35 and Blomquist, A. T.; Maitlis, P. M. J. Am. Chem. Soc. 1962, 84, 2329-2334.
174. Pasto, D. J.; Huang, N.-Z.; Eigenbrot, C. W. J. Am. Chem. Soc. 1985, 107, 3160-3172. Hegedus, L. S.; Kambe, N.; Ishii, Y.; Mori, A. J. Org. Chem. 1985, 50, 2240-2243. Stephan, C.; Munz, C.; tom Dieck, H. J. Organomet. Chem. 1994, 468, 273-278. Hughes, R. P.; Powell, J. J. Organomet. Chem. 1969, 20, P17-P19. Broadbent, T. A.; Pringle, G. E. J. Inorg. Nucl. Chem. 1971, 33, 2009-2014. For related palladacycles in the formal oxidation state (IV), see ref 35 and Blomquist, A. T.; Maitlis, P. M. J. Am. Chem. Soc. 1962, 84, 2329-2334.
175. Pasto, D. J.; Huang, N.-Z.; Eigenbrot, C. W. J. Am. Chem. Soc. 1985, 107, 3160-3172. Hegedus, L. S.; Kambe, N.; Ishii, Y.; Mori, A. J. Org. Chem. 1985, 50, 2240-2243. Stephan, C.; Munz, C.; tom Dieck, H. J. Organomet. Chem. 1994, 468, 273-278. Hughes, R. P.; Powell, J. J. Organomet. Chem. 1969, 20, P17-P19. Broadbent, T. A.; Pringle, G. E. J. Inorg. Nucl. Chem. 1971, 33, 2009-2014. For related palladacycles in the formal oxidation state (IV), see ref 35 and Blomquist, A. T.; Maitlis, P. M. J. Am. Chem. Soc. 1962, 84, 2329-2334.
176. Pasto, D. J.; Huang, N.-Z.; Eigenbrot, C. W. J. Am. Chem. Soc. 1985, 107, 3160-3172. Hegedus, L. S.; Kambe, N.; Ishii, Y.; Mori, A. J. Org. Chem. 1985, 50, 2240-2243. Stephan, C.; Munz, C.; tom Dieck, H. J. Organomet. Chem. 1994, 468, 273-278. Hughes, R. P.; Powell, J. J. Organomet. Chem. 1969, 20, P17-P19. Broadbent, T. A.; Pringle, G. E. J. Inorg. Nucl. Chem. 1971, 33, 2009-2014. For related palladacycles in the formal oxidation state (IV), see ref 35 and Blomquist, A. T.; Maitlis, P. M. J. Am. Chem. Soc. 1962, 84, 2329-2334.
177. Jolly, P. W. Angew. Chem. 1985, 97, 279-291; Angew. Chem., Int. Ed. Engl. 1985, 24, 283-295.
178. Jolly, P. W. Angew. Chem. 1985, 97, 279-291; Angew. Chem., Int. Ed. Engl. 1985, 24, 283-295.
179. Lautens, M.; Ren, Y. J. Am. Chem. Soc. 1996, 118, 9597-9605; for a X-ray structure analysis of a related structure, see: Su, C.-C.; Chen, J.-T.; Lee, G.-H., Wang, Y. J. Am. Chem. Soc. 1994, 116, 4999-5000.
180. Lautens, M.; Ren, Y. J. Am. Chem. Soc. 1996, 118, 9597-9605; for a X-ray structure analysis of a related structure, see: Su, C.-C.; Chen, J.-T.; Lee, G.-H., Wang, Y. J. Am. Chem. Soc. 1994, 116, 4999-5000.
181. The formation of palladacyclobutane from palladium(II) carbenoids and olefins has been proposed, see: Taber, D. F.; Amedio, J. C., Jr.; Sherrill, R. G. J. Org. Chem. 1986, 51, 3382-3384. Hoye, T. R.; Dinsmore, C. J.; Johnson, D. S.; Korkowski, P. F. J. Org. Chem. 1990, 55, 4518-4520.
182. The formation of palladacyclobutane from palladium(II) carbenoids and olefins has been proposed, see: Taber, D. F.; Amedio, J. C., Jr.; Sherrill, R. G. J. Org. Chem. 1986, 51, 3382-3384. Hoye, T. R.; Dinsmore, C. J.; Johnson, D. S.; Korkowski, P. F. J. Org. Chem. 1990, 55, 4518-4520.
183. For a recent review on metallacyclobutanes, see: Jennings, P. W.; Johnson, L. L. Chem. Rev. 1994, 94, 2241-2290.
184. The (Z)-enols are always part of an aromatic system, i.e. o-alkynylphenols as substrates: Kundu, N. G.; Pal, M.; Mahanty, J. S.; Dasgupta, S. K. J. Chem. Soc., Chem. Commun. 1992, 41-42. Torii, S.; Xu, L. H.; Okumoto, H. Synlett 1992, 515-516. Candiani, I.; DeBernardinis, S.; Cabri, W.; Marchi, M.; Bedeschi, A.; Penco, S. Synlett 1993, 269-270.
185. The (Z)-enols are always part of an aromatic system, i.e. o-alkynylphenols as substrates: Kundu, N. G.; Pal, M.; Mahanty, J. S.; Dasgupta, S. K. J. Chem. Soc., Chem. Commun. 1992, 41-42. Torii, S.; Xu, L. H.; Okumoto, H. Synlett 1992, 515-516. Candiani, I.; DeBernardinis, S.; Cabri, W.; Marchi, M.; Bedeschi, A.; Penco, S. Synlett 1993, 269-270.
186. The (Z)-enols are always part of an aromatic system, i.e. o-alkynylphenols as substrates: Kundu, N. G.; Pal, M.; Mahanty, J. S.; Dasgupta, S. K. J. Chem. Soc., Chem. Commun. 1992, 41-42. Torii, S.; Xu, L. H.; Okumoto, H. Synlett 1992, 515-516. Candiani, I.; DeBernardinis, S.; Cabri, W.; Marchi, M.; Bedeschi, A.; Penco, S. Synlett 1993, 269-270.
187. Bates, R. W.; Gabel, C. J.; Ji, J.; Rama-Devi, T. Tetrahedron 1995, 51, 8199-8212. Amatore, C.; Blart, E.; Genêt, J. P.; Jutand, A.; Lemaire-Audoire, S. Savignac, M. J. Org. Chem. 1995, 60, 6829-6839.
188. Bates, R. W.; Gabel, C. J.; Ji, J.; Rama-Devi, T. Tetrahedron 1995, 51, 8199-8212. Amatore, C.; Blart, E.; Genêt, J. P.; Jutand, A.; Lemaire-Audoire, S. Savignac, M. J. Org. Chem. 1995, 60, 6829-6839.
189. Utimoto, K. Pure Appl. Chem. 1983, 55, 1845-1852. Fukuda, Y.; Shiragami, H.; Utimoto, K.; Nozaki, H. J. Org. Chem. 1991, 56, 5816-5819.
190. Utimoto, K. Pure Appl. Chem. 1983, 55, 1845-1852. Fukuda, Y.; Shiragami, H.; Utimoto, K.; Nozaki, H. J. Org. Chem. 1991, 56, 5816-5819.
191. Treffers, H. P.; Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 1708-1712. Newman, M. S.; Deno, N. C. J. Am. Chem. Soc. 1951, 73, 3651-3653. Bender, M. L.; Chen, M. C. J. Am. Chem. Soc. 1963, 85, 37-40.
192. Treffers, H. P.; Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 1708-1712. Newman, M. S.; Deno, N. C. J. Am. Chem. Soc. 1951, 73, 3651-3653. Bender, M. L.; Chen, M. C. J. Am. Chem. Soc. 1963, 85, 37-40.
193. Treffers, H. P.; Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 1708-1712. Newman, M. S.; Deno, N. C. J. Am. Chem. Soc. 1951, 73, 3651-3653. Bender, M. L.; Chen, M. C. J. Am. Chem. Soc. 1963, 85, 37-40.
194. Hopf, H. Angew. Chem. 1984, 96, 947-958; Angew. Chem., Int. Ed. Engl. 1984, 23, 948-960.
195. Hopf, H. Angew. Chem. 1984, 96, 947-958; Angew. Chem., Int. Ed. Engl. 1984, 23, 948-960.
196. Spino, C.; Liu, G.; Tu, N.; Girard, S. J. Org. Chem. 1994, 59, 5596-5608 and literature cited therein.
197. The author has deposited atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK