Transition metal catalysis in fluorous media: Practical application of a new immobilization principle to rhodium-catalyzed hydroborations of alkenes and alkynes

Journal of the American Chemical Society

Volumn 121, Issue 12, 1999, Pages 2696-2704

  Juliette, Jerrick J J ^a   Rutherford, Drew ^a,d   Horváth, István T ^b   Gladysz, J A ^a,c  

^a UNIVERSITY OF UTAH   (United States)

^b EXXONMOBIL UPSTREAM RESEARCH COMPANY   (United States)

^c UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^d Université du Québec à Montréal   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; ADDITION REACTIONS; ATOMIC SPECTROSCOPY; CATALYSIS; CATALYSTS; EVAPORATION; EXTRACTION; OLEFINS; RHODIUM; SOLUBILITY; TOLUENE;

ALKYNE; CATALYST IMMOBILIZATION; HYDROBORATIONS;

FLUORINE COMPOUNDS;

ALCOHOL DERIVATIVE; ALKENE; ALKYNE; BORANE DERIVATIVE; ORGANOBORON DERIVATIVE; RHODIUM;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ENGINEERING; CHEMICAL REACTION; COMPLEX FORMATION; SOLUBILITY; SYNTHESIS; THERMOSTABILITY;

EID: 0033620372     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja982955b     Document Type: Article

References (76)

1. (a) Cornils, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 1575; Angew. Chem. 1995, 107, 1709.
2. (a) Cornils, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 1575; Angew. Chem. 1995, 107, 1709.
3. (b) Cornils, B. Angew. Chem., Int. Ed. Engl. 1997, 36, 2057; Angew. Chem. 1997, 109, 2147.
4. (b) Cornils, B. Angew. Chem., Int. Ed. Engl. 1997, 36, 2057; Angew. Chem. 1997, 109, 2147.
5. (a) Horváth, I. T.; Rábai, J. Science 1994, 266, 72.
6. (b) Horváth, I. T.; Rábai, J. U.S. Patent 5,463,082, 1995.
7. (c) Horváth, I. T.; Kiss, G.; Cook, R. A.; Bond, J. E.; Stevens, P. A.; Rabái, J.; Mozeleski, E. J. J. Am. Chem. Soc. 1998, 120, 3133.
8. Juliette, J. J. J.; Horváth, I. T.; Gladysz, J. A. Angew. Chem., Int. Ed. Engl. 1997, 36, 1610; Angew. Chem. 1997, 109, 1682.
9. Juliette, J. J. J.; Horváth, I. T.; Gladysz, J. A. Angew. Chem., Int. Ed. Engl. 1997, 36, 1610; Angew. Chem. 1997, 109, 1682.
10. Rutherford, D.; Juliette, J. J. J.; Rocaboy, C.; Horváth, I.; Gladysz, J. A. Catal. Today 1998, 42, 381.
11. Horváth, I. T. Acc. Chem. Res. 1998, 31, 641.
12. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
13. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
14. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
15. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
16. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
17. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
18. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
19. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
20. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
21. Lead references to other groups now active in fluorous phase catalysis: (a) Klement, I.; Lütjens, H.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J.-M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (d) Ryu, I.; Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P. Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari, F.; Quici, S. J. Chem. Soc., Chem. Commun. 1998, 877. (f) Betzemeier, B.; Lhermitte, F.; Knochel, P. Tetrahedron Lett. 1998, 39, 6667. (g) Kling, R., Sinou, D., Pozzi, G.; Choplin, A.; Quignard, F.; Busch, S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439.
22. (a) Curran, D. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 1174; Angew. Chem. 1998, 110, 1230.
23. (a) Curran, D. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 1174; Angew. Chem. 1998, 110, 1230.
24. (b) Barthel-Rosa, L. P.; Gladysz, J. A. Coord. Chem. Rev. 1999, in press.
25. (a) Minnesota Mining and Manufacturing Co. British Patent 840,725, 1960.
26. (b) Tiers, G. V. D. (Minnesota Mining and Manufacturing Co.). U.S. Patent 3,281,426, Oct 25, 1966.
27. Alvey, L. J.; Rutherford, D.; Juliette, J. J. J.; Gladysz, J. A. J. Org. Chem. 1998, 63, 6302.
28. (a) Most recent review: Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957. (b) Most recent perspective: Wadepohl, H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2441; Angew. Chem. 1997, 109, 2547.
29. (a) Most recent review: Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957. (b) Most recent perspective: Wadepohl, H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2441; Angew. Chem. 1997, 109, 2547.
30. (a) Most recent review: Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957. (b) Most recent perspective: Wadepohl, H. Angew. Chem., Int. Ed. Engl. 1997, 36, 2441; Angew. Chem. 1997, 109, 2547.
31. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
32. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
33. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
34. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
35. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
36. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
37. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
38. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
39. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
40. Lead references to rhodium catalysts: (a) Männig, D.; Nöth, H. Angew. Chem., Int. Ed. Engl. 1985, 24, 878; Angew. Chem. 1985, 97, 854. (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671. (c) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc. 1992, 114, 6679. (d) Westcou, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T. J. Am. Chem. Soc. 1992, 114, 8863. (e) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350. (f) Brown, J. M.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 1994, 116, 866. (g) Pereira, S.; Srebnik, M. J. Am. Chem. Soc. 1996, 118, 909. (h) Schnyder, A.; Togni, A.; Wiesli, U. Organometallies 1997, 16, 255. (i) Garrett, C. E.; Fu, G. C. J. Org. Chem. 1998, 63, 1370.
41. Other 1996-98 literature: (a) He, X.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 1696. (b) Motry, D. H.; Brazil, A. G.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 2743. (c) Lantero, D. R.; Ward, D. L.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 9699. (d) Zaidlewicz, M.; Meller, J. Tetrahedron Lett. 1997, 38, 7279.
42. Other 1996-98 literature: (a) He, X.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 1696. (b) Motry, D. H.; Brazil, A. G.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 2743. (c) Lantero, D. R.; Ward, D. L.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 9699. (d) Zaidlewicz, M.; Meller, J. Tetrahedron Lett. 1997, 38, 7279.
43. Other 1996-98 literature: (a) He, X.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 1696. (b) Motry, D. H.; Brazil, A. G.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 2743. (c) Lantero, D. R.; Ward, D. L.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 9699. (d) Zaidlewicz, M.; Meller, J. Tetrahedron Lett. 1997, 38, 7279.
44. Other 1996-98 literature: (a) He, X.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 1696. (b) Motry, D. H.; Brazil, A. G.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 2743. (c) Lantero, D. R.; Ward, D. L.; Smith, M. R., III. J. Am. Chem. Soc. 1997, 119, 9699. (d) Zaidlewicz, M.; Meller, J. Tetrahedron Lett. 1997, 38, 7279.
45. Dinh, L.; Gladysz, J. A., manuscript in preparation.
46. Guillevic, M.-A.; Rocaboy, C.; Arif, A. M.; Horváth, I. T.; Gladysz, J. A. Organometallics 1998, 17, 707.
47. 11 in exploratory and mechanistic studies. Other perfluoroalkane solvents should serve equally well but are often sold as mixtures of isomers or by boiling point range. This could compromise the reproducibility and interpretation of rate constants, partition coefficients, and related measurements.
48. Fawcett, J.; Hope, E. G.; Kemmitt, R. D. W.; Paige, D. R.; Russell, D. R.; Stuart, A. M.; Cole-Hamilton, D. J.; Payne, M. J. J. Chem. Soc., Chem. Commun. 1997, 1127.
49. 11) shows a gradual tail with a very slight shoulder at 429 nm.
50. 11 at 25°C. we measure ratios of 98.4:1.6 (molar), 94.2:5.8 (mass), and 97.1:2.9 (volume) in the upper organic layer, and 3.8: 96.2, 1.0:99.0, and 2.0:98.0 in the lower fluorous layer (Supporting Information). Since these ratios depend on solutes and temperature, we approximate our biphase systems as immiscible components that retain their original volumes in all calculations.
51. Lane, C. F.; Kabalka, G. W. Tetrahedron 1976, 32, 981.
52. 1H NMR experiments showed the formation of rhodium hydride complexes of limited thermal stability.
53. Brown, H. C.; Gupta, S. K. J. Am. Chem. Soc. 1975, 97, 5249.
54. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
55. (b) Suzuki, A. In Metal-catalyzed Cross-coupling Reactions; Diederieh, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; Chapter 2.
56. Pereira, S.; Srebnik, M. Organometallics 1995, 14, 3127.
57. Tucker, C. E.; Davidson, J.; Knochel, P. J. Org. Chem. 1992, 57, 3482.
58. Westcott, S. A.; Blom, H. P.; Marder, T. B.; Baker, R. T.; Calabrese, J. C. Inorg. Chem. 1993, 32, 2175.
59. Rutherford, D.; Barthel-Rosa, L. P.; Bennett, B. L., work in progress, University of Utah.
60. See ref 7c and the following: (a) Bhattacharyya, P.; Gudmunsen, D.; Hope, E. G.; Kemmitt, R. D.; Paige, D. R.; Stuart, A. M. J. Chem. Soc., Perkin Trans. 1 1997, 3609. (b) Kainz, S.; Koch, D.; Baumann, W.; Leitner, W. Angew. Chem., Int. Ed. Engl. 1997, 36, 1628; Angew. Chem. 1997, 109, 1699.
61. See ref 7c and the following: (a) Bhattacharyya, P.; Gudmunsen, D.; Hope, E. G.; Kemmitt, R. D.; Paige, D. R.; Stuart, A. M. J. Chem. Soc., Perkin Trans. 1 1997, 3609. (b) Kainz, S.; Koch, D.; Baumann, W.; Leitner, W. Angew. Chem., Int. Ed. Engl. 1997, 36, 1628; Angew. Chem. 1997, 109, 1699.
62. See ref 7c and the following: (a) Bhattacharyya, P.; Gudmunsen, D.; Hope, E. G.; Kemmitt, R. D.; Paige, D. R.; Stuart, A. M. J. Chem. Soc., Perkin Trans. 1 1997, 3609. (b) Kainz, S.; Koch, D.; Baumann, W.; Leitner, W. Angew. Chem., Int. Ed. Engl. 1997, 36, 1628; Angew. Chem. 1997, 109, 1699.
63. (a) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373.
64. (b) Burdeniuc, J.; Jedlicka, B.; Crabtree, R. H. Chem. Ber./ Recl. 1997, 130, 145.
65. Marder, T. B.; Norman, N. C. Top. Catal. 1998, 5, 63.
66. Cammenga, H. K.; Epple, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 4, 1171; Angew. Chem. 1995, 107, 1284.
67. Cammenga, H. K.; Epple, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 4, 1171; Angew. Chem. 1995, 107, 1284.
68. Complex 3 remains soluble in hexane at -30°C, and analytically pure samples have not yet been obtained.
69. The resonances were assigned as in footnote 39 of ret 15.
70. 13C (ppm) 148.9, 122.7, 112.5, 39.3, 38.5, 37.0, 32.7, 32.4, 29.4.
71. 3.
72. 3.
73. For the analogous uncatalyzed reaction, see ref 22 and the following: Pelter, A.; Smith, K.; Brown, H. C. In Borane Reagents: Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.; Academic Press: New York, 1988; p 194.
74. For the analogous uncatalyzed reaction, see refs 20 and 22.
75. 22
76. 1H} (ppm) trans at 149.4, 128.8, 128.7, 128.4, 128.0, 126.9, 116.2 (br), 83.1, 24.6, minor at 137.7, 137.3, 130.7, 128.0, 127.0, 125.1, 116.2 (br), 83.5, 21.0.