Reduction of cyclic group 6 Fischer carbene complexes: A case of exquisite regioselectivity

Journal of Organic Chemistry

Volumn 68, Issue 9, 2003, Pages 3538-3545

  Ramírez López, Pedro ^a   Gómez Gallego, Mar ^a   Mancheño, María José ^a   Sierra, Miguel A ^a   Bilurbina, Montse ^b   Ricart, Susagna ^b  

^a UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

^b INSTITUT DE CIÈNCIA DE MATERIALS DE BARCELONA ICMAB CSIC   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

HYDRIDES; REDUCTION; RESONANCE;

AROMATIC RESONANCE;

ORGANIC COMPOUNDS;

CARBENOID;

ANALYTIC METHOD; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; COMPLEX FORMATION; CONTRAST ENHANCEMENT; EXPERIENCE; ISOTOPE LABELING; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0242584838     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0267347     Document Type: Article

References (82)

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55. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
56. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
57. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
58. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
59. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
60. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
61. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
62. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
63. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
64. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
65. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
66. 5M moiety in the reactions of Fischer carbene complexes are scarce: (a) Barluenga, J.; Trabanco, A. A.; Flórez, J.; García-Granda, S.; Llorca, M.-A. J. Am. Chem. Soc. 1998, 120, 12129. (b) Fischer, H.; Schlageter, A.; Bidell, W.; Früh, A. Organometallics 1991, 10, 389. (c) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc. 1989, 111, 9194. (d) Maxey, C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L. J. Am. Chem. Soc. 1992, 114, 5153. See also ref 11. In contrast, 1,2-migrations are more common: (e) Fischer, H.; Meisner, T.; Hofmann, J. Chem Ber. 1990, 123, 1799. (f) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486. (g) Iwasawa, N.; Maeyama, K. J. Org. Chem. 1997, 62, 1918. (h) Iwasawa, N.; Ochiai, T.; Maeyama, K. Organometallics 1997, 16, 5137. (i) Iwasawa, N.; Ochiai, T.; Maeyama, K. J. Org. Chem. 1998, 63, 3164. (j) Barluenga, J.; Tomás, M.; Ballesteros, A.; Santamaria, J.; López-Ortiz, F.; Carbajo, R.; García-Granda, S.; Pertierra, P. Chem. Eur. J. 1996, 2, 88. (k) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pertierra, P. J. Am. Chem. Soc. 1996, 118, 695. (l) Barluenga, J.; Tomás, M.; Rubio, E.; López-Pelegrín, J. A.; García-Granda, S.; Pérez-Priede, M. J. Am. Chem. Soc. 1999, 121, 3065.
67. 6 in the presence of acetyl chloride. See: Berke, H.; Härter, P.; Huttner, G.; v. Seyerl, J. J. Organomet. Chem. 1981, 219, 317.
68. Elguero, J.; Marzin, C.; Katritzky, A. R.; Linda, P. In The Tautomerism of Heterocycles, Advances in Heterocyclic Chemistry; Katritzky, A. R., Boulton, A. J., Eds.; Academic Press: New York, 1976; Suppl. 1.
69. Sierra, M. A.; del Amo, J. C.; Mancheño, M. J.; Gómez-Gallego, M.; Torres, M. R. Chem. Commun. 2002, 1842.
70. PM3-calculations were effected using Chem 3D Pro 6.0 program.
71. We have already proposed (ref 11a) the participation of these π-allyl species in the reduction of open-chain group 6 metal-carbene complexes. However, until now no direct experimental evidence about its participation in the reduction processes of group 6 metal-carbene complexes was obtained.
72. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
73. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
74. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
75. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
76. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
77. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
78. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
79. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez- Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
80. 3-allyl complexes are scarce, their role as intermediates in diverse reactions of chromium(0) carbene complexes has been repeatedly proposed. (d) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 1999, 309. (e) Hoffmann, M.; Reissig, H.-U. Synlett 1995, 625. (f) Harvey, D. F.; Lund, K. P. J. Am. Chem. Soc. 1991, 113, 8916. (g) Buchert, M.; Reissig, H.-U. Chem. Ber. 1992, 125, 2723. (h) Sakurai, H.; Tanabe, K.; Narasaka, K. Chem. Lett. 2000, 168. The participation of oxa-allyl intermediates in the rearrangement of carbon-centered pentacarbonylchromium enolates to oxygen-centered enolates has been shown using DFT calculations, see: (h) Arrieta, A.; Cossío, F. P.; Fernández, I.; Gómez-Gallego, M.; Lecea, B.; Mancheño, M. J.; Sierra, M. A. J. Am. Chem. Soc. 2000, 122, 11509.
81. The rearrangement of bis-alkene tetracarbonyl complexes of tungsten to π-allyl hydrides is a prototypical reaction in the catalytic isomerization and methatesis of olefins. For a review, see: Szyman-skabuzar, T. Coord. Chem. Rev. 1997, 159, 205.
82. 1H NMR spectra of the crude reaction mixtures. However, we have been unable to obtain these compounds with a degree of purity enough to effect an unambiguous structural characterization.