Dichloromethane as an unusual methylene equivalent. A new entry of highly nucleophilic and selective titanium-methylene complexes for ester methylenation

Organic Letters

Volumn 6, Issue 26, 2004, Pages 4965-4967

  Yan, Tu Hsin ^a   Chien, Ching Ting ^a   Tsai, Chia Chung ^a   Lin, Kuo Wei ^a   Wu, Yen Hsien ^a  

^a NATIONAL CHUNG HSING UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE; CARBENOID; CARBOXYLIC ACID DERIVATIVE; DICHLOROMETHANE; ESTER DERIVATIVE; TITANIUM DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; COMPLEX FORMATION; METHYLATION; QUANTUM YIELD; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 12344331424     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol047887e     Document Type: Article

References (21)

1. (a) Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Chem. Soc. 1978, 100, 3611.
2. (b) Pine, S. H.; Zahier, R.; Evans, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 1980, 102, 3270.
3. (c) Cannizzo, L. F.; Grubs, R. H. J. Org. Chem. 1985, 50, 2316.
4. (d) Pine, S. H.; Petti, R. J.; Geib, G. D.; Cruz, S. G.; Gallego, C. H.; Tijerina, T.; Pine, R. D. J. Org. Chem. 1985, 50, 1212.
5. Petasis, N. A.; Bzoweej, E. I. J. Am. Chem. Soc. 1990, 112, 6392.
6. Matsubara, S.; Ukai, K.; Mizuno, T.; Utimoto, K. Chem. Lett. 1999, 825.
7. For some examples of alkylidenation of ester carbonyl groups, see: (a) Clift, S. M.; Schwartz, J. J. Am. Chem. Soc. 1984, 106, 8300. (b) Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410. (c) Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668. For some examples of ester-methylenation using the Takai protocol, see: Cox, J. M.; Rainier, J. D. Org. Lett. 2001, 2919. Postema, M. H. D.; Piper, J. L. Org. Lett. 2003, 1721. (d) Takeda, T.; Sasaki, R.; Fujiwara, T. J. Org. Chem. 1998, 63, 7286.
8. For some examples of alkylidenation of ester carbonyl groups, see: (a) Clift, S. M.; Schwartz, J. J. Am. Chem. Soc. 1984, 106, 8300. (b) Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410. (c) Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668. For some examples of ester-methylenation using the Takai protocol, see: Cox, J. M.; Rainier, J. D. Org. Lett. 2001, 2919. Postema, M. H. D.; Piper, J. L. Org. Lett. 2003, 1721. (d) Takeda, T.; Sasaki, R.; Fujiwara, T. J. Org. Chem. 1998, 63, 7286.
9. For some examples of alkylidenation of ester carbonyl groups, see: (a) Clift, S. M.; Schwartz, J. J. Am. Chem. Soc. 1984, 106, 8300. (b) Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410. (c) Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668. For some examples of ester-methylenation using the Takai protocol, see: Cox, J. M.; Rainier, J. D. Org. Lett. 2001, 2919. Postema, M. H. D.; Piper, J. L. Org. Lett. 2003, 1721. (d) Takeda, T.; Sasaki, R.; Fujiwara, T. J. Org. Chem. 1998, 63, 7286.
10. For some examples of alkylidenation of ester carbonyl groups, see: (a) Clift, S. M.; Schwartz, J. J. Am. Chem. Soc. 1984, 106, 8300. (b) Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410. (c) Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668. For some examples of ester-methylenation using the Takai protocol, see: Cox, J. M.; Rainier, J. D. Org. Lett. 2001, 2919. Postema, M. H. D.; Piper, J. L. Org. Lett. 2003, 1721. (d) Takeda, T.; Sasaki, R.; Fujiwara, T. J. Org. Chem. 1998, 63, 7286.
11. For some examples of alkylidenation of ester carbonyl groups, see: (a) Clift, S. M.; Schwartz, J. J. Am. Chem. Soc. 1984, 106, 8300. (b) Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410. (c) Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668. For some examples of ester-methylenation using the Takai protocol, see: Cox, J. M.; Rainier, J. D. Org. Lett. 2001, 2919. Postema, M. H. D.; Piper, J. L. Org. Lett. 2003, 1721. (d) Takeda, T.; Sasaki, R.; Fujiwara, T. J. Org. Chem. 1998, 63, 7286.
12. For some examples of alkylidenation of ester carbonyl groups, see: (a) Clift, S. M.; Schwartz, J. J. Am. Chem. Soc. 1984, 106, 8300. (b) Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410. (c) Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668. For some examples of ester-methylenation using the Takai protocol, see: Cox, J. M.; Rainier, J. D. Org. Lett. 2001, 2919. Postema, M. H. D.; Piper, J. L. Org. Lett. 2003, 1721. (d) Takeda, T.; Sasaki, R.; Fujiwara, T. J. Org. Chem. 1998, 63, 7286.
13. For some other examples of ketone methylenation promoted by metals such as Mo and B, see: (a) Kauffmann, T.; Ennen, B.; Sander, J.; Wieschollek, R. Angew. Chem., Int. Ed. Engl. 1983, 22, 244. (b) Pelter, A.; Singaram, B.; Wilson, J. W. Tetrahedron Lett. 1983, 24, 635.
14. For some other examples of ketone methylenation promoted by metals such as Mo and B, see: (a) Kauffmann, T.; Ennen, B.; Sander, J.; Wieschollek, R. Angew. Chem., Int. Ed. Engl. 1983, 22, 244. (b) Pelter, A.; Singaram, B.; Wilson, J. W. Tetrahedron Lett. 1983, 24, 635.
15. For some examples of novel inorganic Grignard reagents, see: (a) Aleandri, L. E.; Bogdanovic, B.; Gaidies, A.; Jones S. Liao, D. J.; Michalowicz, A.; Roziere, J.; Schott, A. J. Organomet. Chem. 1993, 459, 87. (b) Kornowski, A.; Giersig, M.; Vogel, R.; Chemseddine, A.; Weller, H. Adv. Matter. 1993, 5, 634. (c) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. J. J. Org. Chem. 1982, 47, 248. (d) Sobota, P.; Jezowska-Trzebiatowska, B. Coord. Chem. Rev. 1978, 26, 71.
16. For some examples of novel inorganic Grignard reagents, see: (a) Aleandri, L. E.; Bogdanovic, B.; Gaidies, A.; Jones S. Liao, D. J.; Michalowicz, A.; Roziere, J.; Schott, A. J. Organomet. Chem. 1993, 459, 87. (b) Kornowski, A.; Giersig, M.; Vogel, R.; Chemseddine, A.; Weller, H. Adv. Matter. 1993, 5, 634. (c) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. J. J. Org. Chem. 1982, 47, 248. (d) Sobota, P.; Jezowska-Trzebiatowska, B. Coord. Chem. Rev. 1978, 26, 71.
17. For some examples of novel inorganic Grignard reagents, see: (a) Aleandri, L. E.; Bogdanovic, B.; Gaidies, A.; Jones S. Liao, D. J.; Michalowicz, A.; Roziere, J.; Schott, A. J. Organomet. Chem. 1993, 459, 87. (b) Kornowski, A.; Giersig, M.; Vogel, R.; Chemseddine, A.; Weller, H. Adv. Matter. 1993, 5, 634. (c) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. J. J. Org. Chem. 1982, 47, 248. (d) Sobota, P.; Jezowska-Trzebiatowska, B. Coord. Chem. Rev. 1978, 26, 71.
18. For some examples of novel inorganic Grignard reagents, see: (a) Aleandri, L. E.; Bogdanovic, B.; Gaidies, A.; Jones S. Liao, D. J.; Michalowicz, A.; Roziere, J.; Schott, A. J. Organomet. Chem. 1993, 459, 87. (b) Kornowski, A.; Giersig, M.; Vogel, R.; Chemseddine, A.; Weller, H. Adv. Matter. 1993, 5, 634. (c) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. J. J. Org. Chem. 1982, 47, 248. (d) Sobota, P.; Jezowska-Trzebiatowska, B. Coord. Chem. Rev. 1978, 26, 71.
19. Yan, T.-H.; Tsai, C.-C.; Chien, C.-T.; Cho, C.-C.; Huang, P.-C. Org. Lett. 2004, 6, 4961.
20. In the case of benzyl formate as substrate, the desired benzyl viny ether was found to be admixed with significant amounts (>75%) of benzyl alcohol derived from viny ether hydrolysis.
21. New compounds have been characterized spectroscopically.