Michael reaction of stabilized carbon nucleophiles catalyzed by [RuH2(PPh3)4]

Journal of the American Chemical Society

Volumn 118, Issue 36, 1996, Pages 8553-8565

  Gómez Bengoa, Enrique ^a   Cuerva, Juan M ^a   Mateo, Cristina ^a   Echavarren, Antonio M ^a  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

MALONIC ACID DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0029796652     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961373w     Document Type: Article

References (180)

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8. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
9. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
10. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
11. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
12. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
13. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
14. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
15. For recent lead references on Michael reactions of activated nucleophiles, see: (a) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104. (b) Ozaki, Y.; Kubo, A.; Okamura, K.; Kim, S.-W. Chem. Pharm. Bull. 1995, 43, 734. (c) Sasai, H.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1994, 116, 1571. (d) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Pesci, S.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (e) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992. 33, 8073. (f) Antonioletti, R.; Bonadies, F.; Monteagudo, E. S.; Scettri, A. Tetrahedron Lett. 1991, 32, 5373. (g) Ranu, B. C.; Bhar, S.; Sarkar, D. C. Tetrahedron Lett. 1991, 32, 2811. (h) Botteghi, C.; Schianato, A.; Rosini, C.; Salvadori, P. J. Mol. Catal. 1990, 63, 155. (i) Koerner, M.; Rickborn, B. J. Org. Chem. 1990, 55, 2662.
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66. Cationic complexes of type 55 retain the axial triphenylphosphine ligands in the reactions with alkynes, carbon monoxide, or isocyanides: (a) See ref 34. (b) Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J. J. Organomet. Chem. 1990, 390, C57. (c) Echavarren, A. M., López, J.; Santos, A.; Romero, A.; Hermoso, J. A.; Vegas, A. Organometallics 1991, 10, 2371. (d) Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J.; Romero, A. J. Organomet. Chem. 1992, 426, 383.
67. Cationic complexes of type 55 retain the axial triphenylphosphine ligands in the reactions with alkynes, carbon monoxide, or isocyanides: (a) See ref 34. (b) Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J. J. Organomet. Chem. 1990, 390, C57. (c) Echavarren, A. M., López, J.; Santos, A.; Romero, A.; Hermoso, J. A.; Vegas, A. Organometallics 1991, 10, 2371. (d) Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J.; Romero, A. J. Organomet. Chem. 1992, 426, 383.
68. Cationic complexes of type 55 retain the axial triphenylphosphine ligands in the reactions with alkynes, carbon monoxide, or isocyanides: (a) See ref 34. (b) Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J. J. Organomet. Chem. 1990, 390, C57. (c) Echavarren, A. M., López, J.; Santos, A.; Romero, A.; Hermoso, J. A.; Vegas, A. Organometallics 1991, 10, 2371. (d) Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J.; Romero, A. J. Organomet. Chem. 1992, 426, 383.
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95. (a) Komiya, S.; Yamamoto, A.; Ikeda, S. J. Organomet. Chem. 1972, 42, C65.
96. (b) Komiya, S.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1976, 49, 2553.
97. (c) Carrondo, M.; Chaudret, B. N.; Cole-Hamilton, D. J.; Skapski, A. C.; Wilkinson, G. J. Chem. Soc., Chem. Commun. 1978, 463.
98. (d) Chaudret, B. N.; Cole-Hamilton, D. J.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1978, 1739.
99. (e) Rosete, R. O.; Cole-Hamilton, D. J.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1984, 2067.
100. 2=CHPh)2(PPh3)2] with other alkenes, see: (a) Chaudret, B. N.; Cole-Hamilton, D. J.; Wilkinson, G. Acta Chem. Scand., Ser. A 1979, 32, 763. (b) Reference 52d.
101. 2=CHPh)2(PPh3)2] with other alkenes, see: (a) Chaudret, B. N.; Cole-Hamilton, D. J.; Wilkinson, G. Acta Chem. Scand., Ser. A 1979, 32, 763. (b) Reference 52d.
102. 50
103. 2]: (a) Sustmann, R.; Patzke, B.; Boese, R. J. Organomet. Chem. 1994, 470, 191. (b) See also: Patzke, B.; Sustmann, R. J. Organomet. Chem. 1994, 480, 65.
104. 2]: (a) Sustmann, R.; Patzke, B.; Boese, R. J. Organomet. Chem. 1994, 470, 191. (b) See also: Patzke, B.; Sustmann, R. J. Organomet. Chem. 1994, 480, 65.
105. (a) Cole-Hamilton, D. J.; Wilkinson, G. Nouv. J. Chim. 1977, 1. 141.
106. (b) Smith, A. E. Inorg. Chem. 1972, 11, 2306.
107. (c) Komiya, S.; Yamamoto, A. J. Organomet. Chem. 1975, 87, 333.
108. (d) Komiya, S.; Ito, T.; Cowie, M.; Yamamoto, A.; Ibers, J. A. J. Am. Chem. Soc. 1976, 98, 3875.
109. (e) Komiya, S.; Aoki, Y.; Mizuno, Y.; Oyasato, N. J. Organomet. Chem. 1993, 463, 179.
110. (a) Ito, T.; Kitazume, S.; Yamamoto, A.; Ikeda, S. J. Am. Chem. Soc. 1970, 92, 3011.
111. (b) Yamamoto, A.; Ikeda, S. J. Macromol. Sci.-Chem. 1975, A9, 931.
112. 4] initiates the rapid polymerization of acrylonitrile, methacrylonitrile, and methyl vinyl ketone: Rappert, T.; Yamamoto, A. Organometallics 1994, 13, 4984.
113. 55a
114. 41a
115. 4] undergoes elimination at > 180 °C: Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492.
116. 2] (dmpe = 1,2-bis(dimethylphosphino)ethane) requires ca. 140 °C: Hsu, G. C.; Kosar, W. P.; Jones, W. D. Organometallics 1994, 13, 385.
117. 3] (52) was heated at 120 °C for 1.5 h: Kakiuchi, F.; Sekine, S.; Tanaka. Y.; Kamatani, A.; Sonoda, M.; Chatani, N.; Murai, S. Bull. Chem. Soc. Jpn. 1995, 68, 62.
118. 3: Miyakoshi, T. Yakugaku Zasshi 1988, 37, 19; Chem. Abstr. 1988, 109, 92232x.
119. 3: Miyakoshi, T. Yakugaku Zasshi 1988, 37, 19; Chem. Abstr. 1988, 109, 92232x.
120. 3: Miyakoshi, T. Yakugaku Zasshi 1988, 37, 19; Chem. Abstr. 1988, 109, 92232x.
121. 3: Miyakoshi, T. Yakugaku Zasshi 1988, 37, 19; Chem. Abstr. 1988, 109, 92232x.
122. 3: Miyakoshi, T. Yakugaku Zasshi 1988, 37, 19; Chem. Abstr. 1988, 109, 92232x.
123. (a) Trost, B. M.; Schmidt, T. J. Am. Chem. Soc. 1988, 110, 2301.
124. (b) Ma, D.; Lin, Y.; Lu, X.; Yu, Y. Tetrahedron Lett. 1988, 29, 1045.
125. (c) Ma. D.; Yu, Y.; Lu, X. J. Org. Chem. 1989, 54, 1105.
126. (d) Guo, C.; Lu, X. Tetrahedron Lett. 1991, 32, 7549.
127. (a) Trost, B. M.; Kazmaier, U. J. Am. Chem. Soc. 1992, 114, 7933.
128. (b) Guo, C.; Lu, X. J. Chem. Soc., Perkin Trans. 1 1993, 1921. See also:
129. (c) Trost, B. M.; Li, C.-J. J. Am. Chem. Soc. 1994, 116, 3167.
130. (d) Trost, B. M.; Li, C.-J. J. Am. Chem. Soc. 1994, 116, 10819.
131. (e) Zhang, C.; Lu, X. Synlett 1995, 645.
132. Formation of the Michael adduct between methanol and acrylonitrile in a cobalt carbonyl-catalyzed hydrocarbonylation reaction has also been explained as a phosphine-catalyzed process: Dubois, R. A.; Garrou, P. E. J. Organomet. Chem. 1984, 241, 69.
133. The zwitterionic intermediate has been trapped with several electrophiles: (a) Ohmori, H.; Takanami, T.; Shimada, H.; Masui. M. Chem. Pharm. Bull. 1987, 35, 2558. (b) Cristau, H. J.; Torreilles, E.; Barois-Gacherieu, C. Synth. Commun. 1988. 18, 185. (c) Viala, J.; Santelli, M. Synthesis 1988, 370.
134. The zwitterionic intermediate has been trapped with several electrophiles: (a) Ohmori, H.; Takanami, T.; Shimada, H.; Masui. M. Chem. Pharm. Bull. 1987, 35, 2558. (b) Cristau, H. J.; Torreilles, E.; Barois-Gacherieu, C. Synth. Commun. 1988. 18, 185. (c) Viala, J.; Santelli, M. Synthesis 1988, 370.
135. The zwitterionic intermediate has been trapped with several electrophiles: (a) Ohmori, H.; Takanami, T.; Shimada, H.; Masui. M. Chem. Pharm. Bull. 1987, 35, 2558. (b) Cristau, H. J.; Torreilles, E.; Barois-Gacherieu, C. Synth. Commun. 1988. 18, 185. (c) Viala, J.; Santelli, M. Synthesis 1988, 370.
136. Nucleophilic phosphines catalyze the addition of electrophilic alkenes to aldehydes (Baylis-Hillman reaction). For lead references, see: (a) Roth, F.; Gygax, P.; Fráter, G. Tetrahedron Lett. 1992, 33, 1045. (b) Amri, H.; Rambaud, M.; Villieras, J. Tetrahedron Lett. 1989, 30, 7381. (c) Miyakoshi, T.; Saito, S. Nippon Kaguku Kaishi 1983, 1623; Chem. Abstr. 1984, 100, 156191g. (d) For a rhodium(I)- or ruthenium(II)-catalyzed process, see: Sato, S.; Matsuda. I.; Shibata, M. J. J. Organomet. Chem. 1989, 377, 347.
137. Nucleophilic phosphines catalyze the addition of electrophilic alkenes to aldehydes (Baylis-Hillman reaction). For lead references, see: (a) Roth, F.; Gygax, P.; Fráter, G. Tetrahedron Lett. 1992, 33, 1045. (b) Amri, H.; Rambaud, M.; Villieras, J. Tetrahedron Lett. 1989, 30, 7381. (c) Miyakoshi, T.; Saito, S. Nippon Kaguku Kaishi 1983, 1623; Chem. Abstr. 1984, 100, 156191g. (d) For a rhodium(I)- or ruthenium(II)-catalyzed process, see: Sato, S.; Matsuda. I.; Shibata, M. J. J. Organomet. Chem. 1989, 377, 347.
138. Nucleophilic phosphines catalyze the addition of electrophilic alkenes to aldehydes (Baylis-Hillman reaction). For lead references, see: (a) Roth, F.; Gygax, P.; Fráter, G. Tetrahedron Lett. 1992, 33, 1045. (b) Amri, H.; Rambaud, M.; Villieras, J. Tetrahedron Lett. 1989, 30, 7381. (c) Miyakoshi, T.; Saito, S. Nippon Kaguku Kaishi 1983, 1623; Chem. Abstr. 1984, 100, 156191g. (d) For a rhodium(I)- or ruthenium(II)-catalyzed process, see: Sato, S.; Matsuda. I.; Shibata, M. J. J. Organomet. Chem. 1989, 377, 347.
139. Nucleophilic phosphines catalyze the addition of electrophilic alkenes to aldehydes (Baylis-Hillman reaction). For lead references, see: (a) Roth, F.; Gygax, P.; Fráter, G. Tetrahedron Lett. 1992, 33, 1045. (b) Amri, H.; Rambaud, M.; Villieras, J. Tetrahedron Lett. 1989, 30, 7381. (c) Miyakoshi, T.; Saito, S. Nippon Kaguku Kaishi 1983, 1623; Chem. Abstr. 1984, 100, 156191g. (d) For a rhodium(I)- or ruthenium(II)-catalyzed process, see: Sato, S.; Matsuda. I.; Shibata, M. J. J. Organomet. Chem. 1989, 377, 347.
140. Nucleophilic phosphines catalyze the addition of electrophilic alkenes to aldehydes (Baylis-Hillman reaction). For lead references, see: (a) Roth, F.; Gygax, P.; Fráter, G. Tetrahedron Lett. 1992, 33, 1045. (b) Amri, H.; Rambaud, M.; Villieras, J. Tetrahedron Lett. 1989, 30, 7381. (c) Miyakoshi, T.; Saito, S. Nippon Kaguku Kaishi 1983, 1623; Chem. Abstr. 1984, 100, 156191g. (d) For a rhodium(I)- or ruthenium(II)-catalyzed process, see: Sato, S.; Matsuda. I.; Shibata, M. J. J. Organomet. Chem. 1989, 377, 347.
141. Alternatively, 71 may react with the acceptor to furnish oligomers: (a) Horner, L.: Jugeleit. W.; Klupfel, K. Liebigs Ann. Chem. 1955, 591. 108. (b) Kukhtin, V. A.; Kamai, G.; Sinchenko. L. A. Dokl. Akad. Nauk. S.S.S.R. 1958. 118, 505; Chem. Abstr. 1958, 52, 10956.
142. Alternatively, 71 may react with the acceptor to furnish oligomers: (a) Horner, L.: Jugeleit. W.; Klupfel, K. Liebigs Ann. Chem. 1955, 591. 108. (b) Kukhtin, V. A.; Kamai, G.; Sinchenko. L. A. Dokl. Akad. Nauk. S.S.S.R. 1958. 118, 505; Chem. Abstr. 1958, 52, 10956.
143. Alternatively, 71 may react with the acceptor to furnish oligomers: (a) Horner, L.: Jugeleit. W.; Klupfel, K. Liebigs Ann. Chem. 1955, 591. 108. (b) Kukhtin, V. A.; Kamai, G.; Sinchenko. L. A. Dokl. Akad. Nauk. S.S.S.R. 1958. 118, 505; Chem. Abstr. 1958, 52, 10956.
144. 9
145. a of common phosphines, see: Rahman, M. M.; Liu, H.-Y.; Eriks, K.; Prock, A.; Giering, W. P. Organometallics 1989, 8. 1 and references cited therein.
146. For a recent example that stresses the different catalytic abilities of phosphines and amines, see: Vedejs, E.; Diver, S. T. J. Am. Chem. Soc. 1993, 115, 3358.
147. Cuvigny, T.; Julia, M.; Rolando, C. J. Organomet. Chem. 1985, 285, 395.
148. a of ethyl cyanoacetate (56) in DMSO (25 °C) is 13.1: Bordwell, F. G.; Branca, J. C.; Bares, J. E.; Filler, R. J. Org. Chem. 1988, 53, 780.
149. 22
150. (a) Reference Id. p 210.
151. (b) Cope, A. C.; Holmes, H. L.; House, H. O. Org. React. 1957, 9, 107.
152. In our hands, the Michael addition of 78 to 14 was too slow at -78 °C leading to irreproducible yields of 79 and 80. Control experiments demonstrated that these additions took place during the workup at room temperature.
153. Because of the higher reactivity of malonates with 1 in acetonitrile, the reaction was carried out with 1 equiv of 14 for 2 h at 23 °C (36% yield, 72% based on recovered starting material).
154. For ruthenium(II) C-enolates derived from nitriles, see: (a) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577. (b) Hiraki, K.; Ochi, N.; Kitamura, T.; Sasada, Y.; Shinoda, S. Bull. Chem. Soc. Jpn. 1982, 55, 2356.
155. For ruthenium(II) C-enolates derived from nitriles, see: (a) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577. (b) Hiraki, K.; Ochi, N.; Kitamura, T.; Sasada, Y.; Shinoda, S. Bull. Chem. Soc. Jpn. 1982, 55, 2356.
156. (a) Formation of a rhodium(I) malonate complex, in which the malonate anion was not bound to the metal center, has been recently reported: Grushin, V. V.; Kuznetsov, V. F.; Bensimon. C.; Alper, H. Organometallics 1995, 14, 3927.
157. 2], see: Siedle, A. R.; Newmark, R. A.; Gleason, W. B. J. Am. Chem. Soc. 1986. 108, 767.
158. 2. This deuteration pattern is consistent with either a ruthenium (Scheme 5) or phosphine (Scheme 2) catalyzed reaction. equation presented
159. Chatt, J.; Vallarino, L. M.; Venanzi, L. M. J. Chem. Soc. 1957, 3413.
160. Palladium complex 84 behaves as a phosphine sponge toward phosphine-coordinated palladium(II) complexes: (a) Mateo, C.; Cárdenas, D. J.; Fernández-Rivas, C; Echavarren, A. M. Chem. Eur. J. In press, (b) For a similar observation, see: Gretz, E.; Sen, A. J. Am. Chem. Soc. 1986, 108, 6038.
161. Palladium complex 84 behaves as a phosphine sponge toward phosphine-coordinated palladium(II) complexes: (a) Mateo, C.; Cárdenas, D. J.; Fernández-Rivas, C; Echavarren, A. M. Chem. Eur. J. In press, (b) For a similar observation, see: Gretz, E.; Sen, A. J. Am. Chem. Soc. 1986, 108, 6038.
162. (a) Takahashi, Y.; Ito, T.; Sakai, S.; Ishii, Y. J. Chem. Soc., Chem, Commun. 1970, 1065.
163. (b) Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J. J.; Ibers, J. A. J. Organomet. Chem. 1974, 65, 253.
164. For the reaction between 86 and triphenylphosphine, see: Amatore, C.; Jutand, A.; Khalil, F.; M'Barki, M. A.; Mottier, L. Organometallics 1993, 12, 3168.
165. 30c Similarly, palladium complex 85 did not interfere in this Michael reaction catalyzed by 1 (6 mol %, 23 °C).
166. 6. After ca. 30 min no hydride resonance was observed by IH NMR.
167. 3 (75% yield).
168. For lead references of Michael additions of 1,3-dicarbonyl catalyzed by Lewis acids, see: (a) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (b) Keller, E.; Feringa, B. L. Tetrahedron Lett. 1996, 37, 1879.
169. For lead references of Michael additions of 1,3-dicarbonyl catalyzed by Lewis acids, see: (a) Bonadies, F.; Lattanzi, A.; Orelli, L. R.; Scettri, A. Tetrahedron Lett. 1993, 34, 7649. (b) Keller, E.; Feringa, B. L. Tetrahedron Lett. 1996, 37, 1879.
170. 3 and triphenylphosphine (≥4 equiv per Ru) as the promoting agents.
171. (a) For example, the dienophilic reactivity of phenyl vinyl sulfone (87) is not enhanced by the addition of Lewis acids: Carr, R. V. C.; Paquette, L. A. J. Am. Chem. Soc. 1980, 102, 853.
172. (b) For a review of sulfone chemistry, see: Simpkins, N. S. Sulfones in Organic Synthesis; Pergamon: Oxford, 1993.
173. de Lucchi, O.; Pasquato, L.; Modena, G. Tetrahedron Lett. 1984. 25, 3647.
174. 49a
175. Kagechika, K.; Shibasaki, M. J. Org. Chem. 1991, 56, 4093.
176. (a) Bergbreiter, D. E.; Lalonde, J. J. J. Org. Chem. 1987, 52, 1601.
177. (b) Sasson, Y.; Arrd, O. J. Org. Chem. 1989, 54, 4993.
178. (c) Ballini, R.; Petrini, M. Tetrahedron Lett. 1989, 30, 5329.
179. (d) Turner, M. J.; Luckenbach, L. A.; Turner, E.-L. Synth. Commun. 1986, 16, 1377.
180. Heck, R. F. Palladium Reagents in Organic Synthesis; Academic: Orlando. FL. 1985; p 18.