One-electron reduction of aromatic ketones by low-valent lanthanides. Isolation structural characterization, and reactivity of lanthanide ketyl complexes

Journal of the American Chemical Society

Volumn 120, Issue 4, 1998, Pages 754-766

  Hou, Zhaomin ^a   Fujita, Akira ^b   Zhang, Yugen ^a   Miyano, Takanori ^b   Yamazaki, Hiroshi ^b   Wakatsuki, Yasuo ^a  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

^b CHUO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BENZOPHENONE; KETONE; LANTHANIDE; LANTHANIDE KETYL COMPLEX; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; CONTROLLED STUDY; DRUG SYNTHESIS; HYDROLYSIS; NONHUMAN; OXIDATION;

EID: 0032481338     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973184z     Document Type: Article

References (86)

1. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
2. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
3. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
4. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
5. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
6. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
7. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
8. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
9. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
10. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
11. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
12. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
13. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
14. For reviews on metal ketyl-involved organic synthesis, see: (a) Skrydstrup, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 345. (b) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307. (c) Wirth, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 61. (d) Fürstner, A.; Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442. (e) Molander, G. A. Chem. Rev. 1992, 92, 29. (f) Huffman, J. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 8, Chapter 1.4. (g) Robertson, G. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York. 1991; Vol. 3, Chapter 2.6. (h) McMurry, J. E. Chem. Rev. 1989, 89, 1513. (i) Kahn, B. E.; Riecke, R. T. Chem. Rev. 1988, 88, 733. (j) Pradhan, S. K. Tetrahedron 1986, 42, 6351. (k) Huffman, J. W. Acc. Chem. Res. 1983, 16, 399. (l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405; 1974, 7, 281. (m) House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin: Menlo Park, CA, 1972; Chapter 3.
15. For early examples of the formation of ketyl species, see: (a) Bechman, F.; Paul, T. Justus Liebigs Ann. Chem. 1891, 266, 1. (b) Schlenk, W.; Weichel, T. Ber. Dtsch. Chem. Ges. 1911, 44, 1182. (c) Schlenk, W.; Thal, A. Ber. Dtsch. Chem. Ges. 1913, 46, 2480.
16. For early examples of the formation of ketyl species, see: (a) Bechman, F.; Paul, T. Justus Liebigs Ann. Chem. 1891, 266, 1. (b) Schlenk, W.; Weichel, T. Ber. Dtsch. Chem. Ges. 1911, 44, 1182. (c) Schlenk, W.; Thal, A. Ber. Dtsch. Chem. Ges. 1913, 46, 2480.
17. For early examples of the formation of ketyl species, see: (a) Bechman, F.; Paul, T. Justus Liebigs Ann. Chem. 1891, 266, 1. (b) Schlenk, W.; Weichel, T. Ber. Dtsch. Chem. Ges. 1911, 44, 1182. (c) Schlenk, W.; Thal, A. Ber. Dtsch. Chem. Ges. 1913, 46, 2480.
18. For examples, see: Maruyama, K.; Katagiri, T. J. Am. Chem. Soc. 1986, 108, 6263.
19. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
20. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
21. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
22. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
23. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
24. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
25. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
26. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
27. For examples of spectroscopic studies on metal ketyls, see: (a) Covert, K. J.; Wolczanski, P. T.; Hill, S. A.; Krusic, P. J. Inorg. Chem. 1992, 31, 66. (b) Dams, R.; Malinowski, M.; Westdorp, I.; Geise, H. Y. J. Org. Chem. 1982, 47, 248. (c) Mao, S. W.; Nakamura, K.; Hirota, N. J. Am. Chem. Soc. 1974, 96, 5341. (d) Hirota, N. J. Am. Chem. Soc. 1967, 89, 32. (e) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 2538. (f) Steinberger, N.; Fraenkel, G. K. J. Chem. Phys. 1964, 40, 723. (g) Rieger, P. H.; Fraenkel, G. K. J. Chem. Phys. 1962, 37, 2811. (h) Maki, A. H.; Geske, D. H. J. Am. Chem. Soc. 1961, 83, 1852. (i) Hirota, N.; Weissman, S. I. J. Am. Chem. Soc. 1960, 82, 4424.
28. Coutts, R. S. P.; Wailes, P. C.; Martin, R. L. J. Organomet. Chem. 1971, 50, 145.
29. Klei, E.; Telgen, J. H.; Teuben, J. H. J. Organomet. Chem. 1981, 209, 297.
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32. Hou, Z.; Miyano, T.; Yamazaki, H.; Wakatsuki, Y. J. Am. Chem. Soc. 1995, 117, 4421.
33. Hou, Z.; Fujita, A.; Yamazaki, H.; Wakatsuki, Y. J. Am. Chem. Soc. 1996, 118, 2503.
34. Hou, Z.; Jia, X.; Wakatsuki, Y. Angew. Chem., Int. Ed. Engl. 1997, 36, 1292.
35. Hou, Z.; Fujita, A.; Yamazaki, H.; Wakatsuki, Y. J. Am. Chem. Soc. 1996, 118, 7843.
36. Hou, Z.; Wakatsuki, Y. Chem. Eur. J. 1997, 3, 1005.
37. Professor Takats recently informed us that he and co-workers had succeeded in structurally characterizing a samarium(III) benzophenone ketyl complex which was stabilized by two bulky hydrotris(3,5-dimethylpyrazolyl)borate ligands. Takats, J.; et al. Manuscript in preparation. See also: Takats, J. J. Alloys Compd. 1997, 249, 51.
38. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
39. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
40. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
41. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
42. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
43. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
44. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
45. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
46. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
47. For examples, see: (a) Molander, G. A. McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265. (b) Kawatsura, M.; Dekura, F.; Shirahama, H.; Matsuda, F. Synlett 1996, 373. (c) Matsuda, F. J. Synth. Org. Chem. Jpn. 1995, 53, 987. (d) Kagan, H. B. New J. Chem. 1990, 14, 453. (e) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111, 8236. (f) Fevig, T. L.; Elliott, R. L.; Curran, D. P. J. Am. Chem. Soc. 1988, 110, 5064. (g) Fürstner, A.; Csuk, R.; Rohrer, C.; Weidmann, H. J. Chem. Soc., Perkin Trans. 1 1988, 1729. (h) Fukuzawa, S.; Nakanishi, A.; Fujinami, T.; Sakai, S. J. Chem. Soc., Perkin Trans. 1 1988, 1669. (i) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573. (j) Tabuchi, T.; Kawamura, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986, 27, 3889.
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54. Attempts to characterize these species by NMR spectroscopy were not successful due to the presence of paramagnetic species.
55. 15c The hydrogen atoms (H(1) and H(2)) of the diphenylmethoxy groups in 2 were located by the difference Fourier syntheses.
56. 2 (Ln = Sm, Yb) with benzophenone in THF did not give a structurally characterizable benzophenone ketyl complex either, which yielded light-yellow precipitates after a few weeks.
57. 2 axis passing through the Yb and the oxygen and carbon atoms of the CO group of the ketyl unit.
58. Hou, Z.; Fujita, A.; Yamazaki, H.; Wakatsuki. Y. unpublished result.
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65. -3, R = 0.0716, Rw = 0.0945. Details will be reported elsewhere.
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72. -3.
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81. If HMPA was not used, only a THF-insoluble yellow precipitate was obtained.
82. Hou, Z.; Jia, X.; Wakatsuki, Y. Unpublished results. See also ref 12.
83. 6, 22°C): δ 3.54 (br s, 8 H, THF), 1.28 (br s, 8 H, THF), 0.40 (s, 36 H, NMe).
84. 15c,e
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