Frustrated β-chloride elimination. Selective arene alkylation by α-chloronorbornene catalyzed by electrophilic metallocenium ion pairs

Journal of the American Chemical Society

Volumn 126, Issue 39, 2004, Pages 12528-12540

  Dash, Aswini K ^a   Jensen, Tryg R ^a   Stern, Charlotte L ^a   Marks, Tobin J ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ANALYSIS; AROMATIC COMPOUNDS; CATALYSIS; CATALYST SELECTIVITY; COMPLEXATION; MOLECULAR DYNAMICS; POLYMERIZATION; STEREOCHEMISTRY;

ARENE ALKYLATION; CHLORIDE ELIMINATION; ELECTROPHILES; SINGLE-SITE POLYMERIZATION;

ALKYLATION;

1,4 BIS(1 CHLORO 2 NORBORNYL)BENZENE; ALPHA CHLORONORBORNENE DERIVATIVE; AROMATIC COMPOUND; BENZENE; BENZENE DERIVATIVE; BORON; BUTYL GROUP; CHLORIDE; DEUTERIUM; DIMETHYLZIRCONOCENE; FUNCTIONAL GROUP; METHANE; NITROGEN; NORBORNENE DERIVATIVE; PHENYL GROUP; POLYCYCLIC AROMATIC HYDROCARBON; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SILICONE; TITANIUM; TOLUENE; UNCLASSIFIED DRUG; ZIRCONIUM; ZIRCONIUM DERIVATIVE;

ADDITION REACTION; ALKYLATION; ARTICLE; ARYLATION; BETA CHLORIDE ELLIMINATION; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMOREACTIVITY; CORRELATION SPECTROSCOPY; ELEMENTAL ANALYSIS; ELIMINATION REACTION; GAS CHROMATOGRAPHY; HETERONUCLEAR MULTIPLE BOND CORRELATION SPECTROSCOPY; ION PAIR; MASS SPECTROMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; NUCLEAR OVERHAUSER EFFECT; POLYMERIZATION; REACTION ANALYSIS; STEREOCHEMISTRY; X RAY ANALYSIS;

EID: 4744366133     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja047828w     Document Type: Article

References (215)

1. 0 polymerization catalysis, see the following and references therein: (a) Gibson, V. C.; Spitzmesser, S. K. Chem. Rev. 2003, 103, 283-315.
2. (b) Pedeutour, J.-N.; Radhakrishnan, K.; Cramail, H.; Deffieux, A. Macromol. Rapid Commun. 2001, 22, 1095-1123.
3. (c) Gladysz, J. A., Ed. Chem. Rev. 2000, 100 (special issue on "Frontiers in Metal-Catalyzed Polymerization").
4. (d) Marks, T. J., Stevens, J. C., Eds. Top. Catal. 1999, 7 (special volume on "Advances in Polymerization Catalysis. Catalysts and Processes").
5. (e) Scheirs J.; Kaminsky, W. Metallocene-Based Polyolefins: Preparation, Properties, and Technology; John Wiley & Sons: New York, 1999; Vols. 1 and 2.
6. (f) Kaminsky, W. Metalorganic Catalysts for Synthesis and Polymerization: Recent Results by Ziegler-Natta and Metallocene Investigations; Springer-Verlag: Berlin, 1999.
7. (g) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem., Int. Ed. 1999, 38, 428-447.
8. (h) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598.
9. (i) Jordan, R. F. J. Mol. Catal. 1998, 128 (special issue on "Metallocene and Single Site Olefin Catalysis").
10. (j) Kaminsky, W.; Arndt, M. Adv. Polym. Sci. 1997, 127, 143-187.
11. (k) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270.
12. (l) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170.
13. (a) Jensen, T. R.; Yoon, S. C.; Dash, A. K.; Luo, L.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 14482-14494.
14. (b) Johnson, L.; Bennett, A.; Dobbs, K.; Hauptman, E.; Ionkin, E.; Ittel, S.; McCord, E.; McLain, S.; Radzewich, C.; Yin, Z.; Wang, L.; Wang, Y.; Brookhart, M. Polym. Mater. Sci. Eng. 2002, 86, 319.
15. (c) Youkin, T. R.; Connor, E. F.; Henderson, J. I.; Friedrich, S. K.; Grubbs, R. H.; Bansleben, D. A. Science 2000, 287, 460-462.
16. (d) Boffa, L. S.; Novak, B. M. Chem. Rev. 2000, 100, 1479-1493.
17. (e) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 888-899.
18. (f) Johnson, L. K.; Mecking, S. F.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 267-268.
19. For early-transition-metal-mediated polymerization of polar monomers in which polar groups are suitably protected and/or remote from the olefinic functionality, see: Kesti, M. R.; Coates, G. W.; Waymouth, R. M. J. Am. Chem. Soc. 1992, 114, 9679-9680.
20. Padwa, A. R. Prog. Polym. Sci. 1989, 14, 811-833.
21. (a) Stockland, R. A., Jr.; Foley, S. R.; Jordan, R. F. J. Am. Chem. Soc. 2003, 125, 796-809 and references therein.
22. (b) Foley, S. R.; Stockland, R. A., Jr.; Shen, H.; Jordan, R. F. J. Am. Chem. Soc. 2003, 125, 4350-4361 and references therein.
23. (c) Stockland, R. A., Jr.; Jordan, R. F. J. Am. Chem. Soc. 2000, 122, 6315-6316.
24. 2ScF and propylene via insertion and subsequent β-F elimination; see: Burger, B. Thesis, California Institute of Technology, 1987.
25. 2ZrFCl and ethylene; see: Watson, L. A.; Yandulov, D. V.; Caulton, K. G. J. Am. Chem. Soc. 2001, 123, 603-611.
26. For other reactions of vinyl chloride with early-transition-metal complexes, see: (a) Hanzawa, Y.; Kowase, N.; Taguchi, T. Tetrahedron Lett. 1998, 39, 583-586.
27. (b) Takahashi, T.; Kotora, M.; Fischer, R.; Nishihara, Y.; Nadajima, K. J. Am. Chem. Soc. 1995, 117, 11039-11040.
28. Strazisar, S. A.; Wolczanski, P. T. J. Am. Chem. Soc. 2001, 123, 4728-4740.
29. Boone, H. W.; Athey, P. S.; Mullins, M. J.; Philipp, D.; Muller, R.; Goddard, W. A. J. Am. Chem. Soc. 2002, 124, 8790-8791.
30. nZr-Cl) = 116 kcal/mol, and ΔH = -42 kcal/mol; see: (a) Simoes, J. A. M.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688.
31. (b) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701-7715.
32. For recent computational studies on insertion/β-elimination processes involving vinyl chloride and other polar monomers, see: (a) Cundari, T. R.; Taylor, C. D. Organometallics 2003, 22, 4047-4059.
33. (b) Philipp, D. M.; Muller, R. P.; Goddard, W. A., III; Storer, J.; McAdon, M.; Mullins, M. J. Am. Chem. Soc. 2002, 124, 10198-10210.
34. (c) Michalak, A.; Ziegler, T. J. Am. Chem. Soc. 2001, 123, 12266-12278.
35. For strategies and requirements for β-elimination (of H, alkyl, Cl, etc.) from metal-catalyzed systems, see: (a) The Organometallic Chemistry of Transition Metals; Crabtree, R. H., Ed.; John Wiley & Sons: New York, 2001; Chapter 3, p 51; Chapter 7, p 174.
36. (b) Margl, P. M.; Woo, T. K.; Ziegler, T. Organometallics 1998, 17, 4997-5002.
37. (c) Han, Y.; Deng, L.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 5939-5945.
38. (d) Yoshida, T.; Koga, N.; Morokuma, K. Organometallics 1995, 14, 746-758.
39. (e) Abis, L.; Fiorani, T.; Franciscono, G.; Piemontesi, F.; Resconi, L. J. Am. Chem. Soc. 1992, 114, 1025-1032.
40. Spartan/MM2-1evel molecular modeling studies were carried out using the Spartan '02 windows program (Wavefunction, Inc., Irvine, CA, 2001).
41. Chien, J. C. W.; Tsai, W.-M.; Rausch, M. D. J. Am. Chem. Soc. 1991, 113, 8570-8571.
42. (a) Brown, H. C.; Rao, C. G. J. Org. Chem. 1979, 44, 1348-1349.
43. (b) McDonald, R. N.; Steppel, R. N. J. Am. Chem. Soc. 1970, 92, 5664-5670.
44. Mena, M.; Royo, P.; Serrano, R.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 1989, 8, 476-482.
45. Wolczanski, P. T.; Bercaw, J. E. Organometallics 1982, 1, 793-799.
46. (a) Stevens, J. C.; Timmers, F. J.; Wilson, D. R.; Schmidt, G. F.; Nickias, P. N.; Rosen, R. K.; Knight, G. W.; Lai, S. (Dow Chemical Co.). European Pateat Application EP 0416815 A2, 1991; Chem. Abstr. 1991, 115, 93163.
47. (b) Canich, J. M. (Exxon Chemical Co.). European Patent Application EP 0420436 A1, 1991; Chem. Abstr. 1991, 115, 184145.
48. Samuel, E.; Rausch, M. D. J. Am. Chem. Soc. 1973, 95, 6263-6267.
49. Jia, L.; Yang, X.; Stern, C. L.; Marks, T. J. Organometallics 1997, 16, 842-857.
50. Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
51. Beck, S.; Prosenc, M. H.; Brintzinger, H. H.; Goretzki, R.; Herfert, N.; Fink, G. J. Mol. Catal. A 1996, 111, 67-79.
52. Chen, Y.-X.; Marks, T. J. Organometallics 1997, 16, 3649-3657.
53. SHELXL-97; Sheldrick, 1997.
54. International Tables for X-ray Crystallography; Cromer, D. T., Waber, J. T., Eds.; The Kynoch Press: Birmingham, England, 1974; Vol. IV, Table 2.2 A.
55. Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781-782.
56. Creagh, D. C.; McAuley, W. J. In International Tables for Crystallography; Wilson, A. J. C., Ed.; Kluwer Academic Publishers: Boston, 1992; Vol. C, pp 219-222, Table 4.2.6.8.
57. Creagh, D. C.; Hubbell, J. H. In International Tables for Crystallography; Wilson, A. J. C., Ed.; Kluwer Academic Publishers: Boston, 1992; Vol. C, pp 200-206, Table 4.2.4.3.
58. Shelxtl for WindowsNT: Crystal Structure Analysis Package; Bruker: Madison, WI, 1997.
59. ORTEP-3 for Windows v. 1.075: Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565.
60. (a) Kang, M.; Sen, A.; Zakharov, L.; Rheingold, A. L. J. Am. Chem. Soc. 2002, 724, 12080-12082.
61. (b) Alt, H. G.; Englehardt, H. E. J. Organomet. Chem. 1988, 346, 211-218.
62. (c) Oskam, A.; Shoemaker, G.; Rest, A. J. J. Organomet. Chem. 1986, 304, C13-C16.
63. (d) Drouin, M.; Harrod, J. F. Can. J. Chem. 1985, 63, 353-360.
64. (e) Jesse, A. C.; Stufkens, D. J.; Vrieze, K. Inorg. Chim. Acta 1979, 32, 87-91.
65. (f) Jesse, A. C.; Gijben, H. P.; Stufkens, D. J.; Vrieze, K. Inorg. Chim. Acta 1978, 31, 203-210.
66. (g) Bigorgne, M. J. Organomet. Chem. 1977, 127, 55-85.
67. (h) Ashley-Smith, J.; Douek, Z.; Johnson, B. F. G.; Lewis, J. J. Chem. Soc., Dalton Trans. 1974, 128-133.
68. (i) Tolman, C. A. J. Am. Chem. Soc. 1974, 96, 2780-2789.
69. (j) Quinn, H. W.; VanGilder, R. L. Can. J. Chem. 1971, 49, 1323-1327.
70. (k) Cramer, R. J. Am. Chem. Soc. 1967, 89, 4621-4626.
71. March, J. Advanced Organic Chemistry; John Wiley and Sons: New York, 1985; pp 295-298.
72. (a) Chen, E. Y.; Marks, T. J. Chem. Rev. 2000, 4, 1391-1434.
73. (b) Luo, L.; Marks, T. J. In Topics in Catalysis; Marks, T. J., Stevens, J. C., Eds.; Baltzer Science Publisher: Delft, The Netherlands, 1999; Vol. 7, pp 97-106.
74. Chen, Y.-X.; Metz, M. V.; Li, L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 6287-6305.
75. (a) Koo, K.; Fu, P.-F.; Marks, T. J. Macromolecules 1999, 32, 981-988.
76. (b) Koo, K.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 8791-8802.
77. (c) Koo, K.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 4019-4020.
78. For reviews, see: (a) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270.
79. (b) Grubbs, R. H.; Coates, G. W. Acc. Chem. Res. 1996, 29, 85-93.
80. (c) Bochmann, M. Angew. Chem., Int. Ed. Engl. 1992, 31, 1181-1182.
81. (a) Mohammed, M.; Nele, M.; Al-Humydi, A.; Xin, S.; Stapleton, R. A.; Collins, S. J. Am. Chem. Soc. 2003, 125, 7930-7941.
82. (b) Li, L.; Metz, M. V.; Li, H.; Chen, M.-C.; Marks, T. J. J. Am. Chem. Soc. 2002, 124, 12725-12741.
83. (c) Chen, M.-C.; Marks, T. J. J. Am. Chem. Soc. 2001, 123, 11803-11804.
84. (a) Minieri, G.; Corradini, P.; Zambelli, A.; Guerra, G.; Cavallo, L. Macromolecules 2001, 34, 2459-2468.
85. (b) Williams, E. F.; Murray, M. C.; Baird, M. C. Macromolecules 2000, 33, 261-268.
86. (c) Xu, G.; Cheng, D. Macromolecules 2000, 33, 2825-2831.
87. (d) Grassi, A.; Saccheo, S.; Zambelli, A.; Laschi, F. Macromolecules 1998, 31, 5588-5591.
88. (e) Ready, T. E.; Gurge, R.; Chien, J. C. W.; Rausch, M. D. Organometallics 1998, 17, 5236-5239.
89. (f) Zambelli, A.; Pellecchia, C.; Oliva, L. Macromolecules 1989, 22, 2129-2130.
90. (a) Mahanthappa, M. K.; Waymouth, R. M. J. Am. Chem. Soc. 2001, 123, 12093-12094.
91. (b) Tomotsu, N.; Ishihara, N.; Newman, T. H.; Malanga, M. T. J. Mol. Catal. A 1998, 128, 167-190.
92. (c) Kaminsky, W.; Park, Y. W. Macromol. Rapid Commun. 1995, 16, 343-346.
93. (d) Chien, J. C. W.; Salajka, Z.; Dong, S. Macromolecules 1992, 25, 3199-3203.
94. (a) Longo, P.; Proto, A.; Zambelli, A. Macromol. Chem. Phys. 1995, 196, 3015-3029.
95. (b) Zambelli, A.; Longo, P.; Pellecchia, C.; Grassi, A. Macromolecules 1987, 20, 2035-2037.
96. (c) Ishihara, N.; Kuramoto, M.; Seimiya, T.; Uoi, M. Macromolecules 1986, 19, 2464-2465.
97. n model compounds see: (a) Stoebenau, E. J., III; Jordan, R. F. J. Am. Chem. Soc. 2003, 125, 3222-3223.
98. (b) Carpentier, J.-F.; Maryin, V. P.; Luci, J.; Jordan, R. F. J. Am. Chem. Soc. 2001, 123, 898-909.
99. (c) Brandow, C. G.; Mendiratta, A.; Bercaw, J. E. Organometallics 2001, 20, 4253-4261.
100. (d) Casey, C. P.; Carpenetti, D. W., II.; Sakurai, H. Organometallics 2001, 20, 4262-4265 and references therein.
101. (e) Casey, C. P.; Klein, J. F.; Fagan, M. A. J. Am. Chem. Soc. 2000, 122, 4320-4330.
102. (f) Carpentier, J.-F.; Wu, Z.; Lee, C. W.; Strömberg, S.; Christopher, J. N.; Jordan, R. F. J. Am. Chem. Soc. 2000, 122, 7750-7767.
103. 6 is oriented toward the phenyl substituent.
104. Shimanouchi, H.; Sasada, Y. Acta Crystallogr. 1970, B26, 563-577.
105. (a) Evans, S. V.; Hwang, C.; Trotter, J. J. Acta Crystallogr. 1988, C44, 1457-1459.
106. (b) Doms, L.; Hemelrijk, D. V.; Mieroop, W. V. D.; Lenstra, A. T. H.; Geise, H. J. Acta Crystallogr. 1985, B41, 270-274.
107. (c) Newton, M. G.; Pantaleo, N. S.; Kirbawy, S.; Allinger, N. L. J. Am. Chem. Soc. 1978, 100, 2176-2180.
108. (a) Li, H.; Li, L.; Liable-Sands, L.; Rheingold, A. L.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 10788-10789.
109. (b) Stevens, J. C. In Studies in Surface Science and Catalysis; Soga, K., Terano, M., Eds.; Elsevier: Amsterdam, 1994; Vol. 89, pp 277-284.
110. (a) McKnight A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598.
111. (b) Shaffer, T. D.; Canich, J. M.; Squire, K. R. Macromolecules 1998, 31, 5145-5147.
112. (c) Sernetz, F. G.; Mülhaupt, R.; Amor, F.; Eberle, T.; Okuda, J. J. Polym. Sci., Part A 1997, 35, 1571-1578.
113. (d) Soga, K.; Uozomi, T.; Nakamura, S.; Toneri, T.; Teranishi, T.; Sano, T.; Arai, T. Macromol. Chem. Phys. 1996, 197, 4237-4251.
114. (e) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071-1083.
115. For the use of vinyl chloride as a chain-transfer agent in olefin polymerizations, see: Gaynor, S. G. Macromolecules 2003, 36, 4692-4698.
116. 8, in quantitative yield.
117. (a) Matsukawa, T.; Kiba, R.; Ikeda, T. (Chisso Corp.). Japanese Patent 08208736; Chem Abstr. 1996, 125, 276902.
118. 2/MAO as a photoactivated initiator for free-radical VC polymerization, see: Nagy, S. M.; Krishnamurti, R.; Cocoman, M. K.; Opalinski, W. M.; Smolka, T. F. (Occidental Chemical). WO 9923124 A1; Chem. Abstr. 1999, 130, 338530.
119. (a) Endo, K.; Saitoh, M. Polym. J. 2000, 32, 300-302.
120. (b) Endo, K.; Kaneda, N.; Waku, H.; Saitoh, M.; Emori, N. J. Vinyl Addit. Technol. 2001, 7, 177-183.
121. For studies using phenols as radical inhibitors, see: (a) Haddleton, D. M.; Shooter, A. J.; Heming, A. M.; Crossman, M. C.; Duncalf, D. J.; Morsley, S. R. ACS Symp. Ser. 1998, 685, 284-295.
122. (b) Matyjaszewski, K. Macromolecules 1998, 31, 4710-4717.
123. (c) Lartigue-Peyrou, F. Ind. Chem. Libr. 1996, 8, 489-505.
124. (d) Matsumoto, A.; Yamagishi, K.; Aoki, S. J. Polym. Sci., Part A: Polym. Chem. 1994, 32, 917-928.
125. (e) Tudos, F.; Foldes-Berezsnich, T. Prog. Polym. Sci. 1989, 14, 717-761.
126. For the use of 2,6-di-tert-butylphenol as a radical inhibitor in single-site olefin polymerization without compromising activity, see: (a) Mullin, M. J.; Nickias, P. N.; Soto, J. (Dow Chemical Co.). Application WO 97-US 15095 19970827, 1997.
127. (b) Wilen, C.-E.; Nasman, J. H. Macromolecules 1994, 27, 4051-4057.
128. For the effect of 2,6-di-tert-butylphenol derivatives on cationic Fe-catalyzed alkane functionalization in a mechanistic study, see: Kojima, T.; Leising, R. A.; Yan, S.; Que, L. Jr. J. Am. Chem Soc. 1993, 115, 11328-11335.
129. For analogous Ir- and Rh-catalyzed reactions, see: Booth, B. L.; Haszeldine, R. N.; Neuss, G. R. H. J. Chem. Soc., Perkin Trans. 1975, 209-212.
130. - remains ill-defined. For examples of the use of such catalysts, see: (a) Nomura, K.; Fudo, A. J. Mol. Catal. A 2004, 209, 9-17.
131. (b) Nomura, K.; Fudo, A. Inorg. Chim. Acta. 2003, 345, 37-43.
132. (c) Nomura, K.; Fudo, A. Catal. Commun. 2003, 4, 269-274.
133. (d) Nomura, K.; Oya, K.; Komatsu, T.; Imanishi, Y. Macromolecules 2000, 33, 3187-3189.
134. (e) Nomura, K.; Naga, N.; Miki, M.; Yanagi, K.; Imai, A. Organometallics 1998, 17, 2152-2154.
135. (a) Baird, M. C. Chem. Rev. 2002, 100, 1471-1478.
136. (b) Ewart, S. W.; Baird, M. C. In Topics in Catalysis; Marks, T. J., Stevens, J. C., Eds.; Baltzer Science Publisher: Delft, The Netherlands, 1999; Vol. 7, pp 1-8.
137. + cation to the trityl radical, which undergoes subsequent dimerization to Gomberg's dimer, has been reported: Hembre, R. T.; McQueen, J. S. Angew. Chem., Int. Ed. Engl. 1997, 36, 65-67.
138. + cation, see: (a) Jernakoff, P.; Cooper, N. J. Organometallics 1986, 5, 747-751.
139. (b) Zador, E.; Warman, J. M.; Hummel, A. J. Chem. Soc., Faraday Trans. 1979, 75, 914-920.
140. (c) Berlin, K. D.; Shupe, R. D.; Grigsby, R. D. J. Org. Chem. 1969, 34, 2500-2503.
141. (a) Acar, M.; Kucukoner, M. Polymer 1997, 38, 2829-2833.
142. (b) Gonzalez, M.; Rodriguez, M.; Leon, L. M. J. Macromol. Sci., Pure Appl. Chem. 1995, A32, 1773-1780.
143. (c) Velichkova, R.; Panayotov, I. M.; Doicheva, J. J. Polym. Sci., Polym. Chem. Ed. 1982, 20, 2895-2902.
144. (d) Florquin, S. M.; Goethals, E. J. Makromol. Chem. 1981, 182, 3371-3377.
145. (e) Richey, H. G.; Lustgarten, R. K.; Richey, J. M. J. Org. Chem. 1968, 33, 4543-4545.
146. March, J. Advanced Organic Chemistry; John Wiley and Sons: New York, 1992; pp 501-568.
147. (a) Carr, A. G.; Dawson, D.; Bochmann, M. Macromolecules 1998, 31, 2035-2040.
148. (b) Blanco, S. G.; Sal, M. P. G.; Carreras, S. M.; Mena, M.; Royo, P.; Serrano, R. J. Chem. Soc., Chem. Commun. 1986, 1572-1573.
149. (c) Wailes, P. C.; Coutts, R. S. P.; Weigold, H. Organometallic Chemistry of Titanium, Zirconium and Hafnium; Academic Press: New York, 1974; p 132.
150. (a) Ryu, J. S.; Li, G. R.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 12584-12605.
151. (b) Hong, S.; Marks, T. J. J. Am. Chem. Soc. 2002, 124, 7886-7887.
152. (c) Jeske, G.; Lauke, H.; Mauermann, H.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8091-8103.
153. - activated system in a 1:1 stoichiometric molar ratio followed by addition of 1.0 equiv of α-chloronorbornene evidences no inhibition of catalytic turnover and thus argues against any significant role of H+ initiation as a competing pathway to product formation. For related studies, see: (a) Barsan, F.; Karam, A. R.; Parent, M. A.; Baird, M. C. Macromolecules 1998, 31, 8439-8447.
154. (b) Shaffer, T. D.; Ashbaugh, J. R. J. Polym. Sci., Part A: Polym. Chem. 1997, 35, 329-344.
155. For reviews of Friedel-Crafts alkylation reactions, see, for example: (a) Olah, G. A.; Krishnamurti, R.; Prakash, G. K. S. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 3, Chapter 1.8, p 293.
156. (b) Roberts, R. M.; Khalaf, A. A. Friedel-Crafts Alkylation Chemistry: A Century of Discovery; Marcel Dekker: New York, 1984.
157. (c) Friedel-Crafts Chemistry; Olah, G. A., Ed.; Wiley: New York, 1973.
158. (d) Friedel-Crafts and Related Reactions; Olah, G. A., Ed.; Wiley-Interscience: New York, 1963-65; Vols. 1-4.
159. (e) Friedman, H. M.; Nelson, A. L. J. Org. Chem. 1969, 34, 3211-3213.
160. (a) Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2001, 40, 160-163,
161. (b) Zhuang, W.; Gathergood, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2001, 66, 1009-1013.
162. (c) Gathergood, N.; Zhuang, W.; Jørgensen, K. A. J. Am. Chem. Soc. 2000, 122, 12517-12522.
163. Olah, G. A.; Lee, C. S.; Surya Prakash, G. K. J. Org. Chem. 1994, 59, 2590-2593.
164. Lewis acid-initiated alkylation at the bridgehead position of 1-chloronorbornane occurs readily to afford the corresponding 1-aryl-substituted norbornane; see: Olah, G. A.; Lee, C. S.; Prakash, G. K. S.; Moriarty, R. M.; Rao, M. S. C. J. Am. Chem. Soc. 1993, 115, 10728-10732.
165. (a) Lipian, J.; Mimna, R. A.; Fondran, J. C.; Yandulov, D.; Shick, R. A.; Goodall, B. L.; Rhodes, L. F. Macromolecules 2002, 35, 8969-8977.
166. (b) Hasan, T.; Nishii, K.; Shiono, T.; Ikeda, T. Macromolecules 2002, 35, 8933-8935.
167. (c) Janiak, C.; Lassahn, P. G. J. Mol. Catal. 2001, 166, 193-209 and references therein.
168. (d) Hennis, A. D.; Polley, J. D.; Long, G. S.; Sen, A.; Yandulov, D.; Lipian, J.; Benedikt, G. M.; Rhodes, L. F.; Huffman, J. Organometallics 2001, 20, 2802-2812.
169. (e) Sakai, T.; Novak, B. M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2001, 42, 419-420.
170. (f) Peucker, U.; Heitz, W. Macromol. Rapid Commun. 1998, 19, 159-162.
171. (g) Jeremic, D.; Wang, Q.; Quyoum, R.; Baird, M. C. J. Organomet. Chem. 1995, 497, 143-147.
172. (h) Mehler, C.; Risse, W. Macromolecules 1992, 25, 4226-4228.
173. (i) Kaminsky, W.; Bark, A.; Amdt, M. Macromol. Chem., Macromol. Symp. 1991, 47, 83-93.
174. For computational studies on the addition of norbornene to cationic metal species, see: (a) Kim, K. H.; Han, Y.-K.; Lee, S. U.; Chun, S.-H.; Ok, J. H. J. Mol. Model. 2003, 9, 304-307.
175. (b) Yoshida, Y.; Nakano, T.; Tanaka, H.; Fujita, T. lsr. J. Chem. 2002, 42, 353-359.
176. (a) Tritto, I.; Boggioni, L.; Jansen, J. C.; Thorshaug, K.; Sacchi, M. C.; Ferro, D. R. Macromolecules 2002, 35, 616-623.
177. (b) Wendt, R. A.; Fink, G. Macromol. Chem. Phys. 2001, 202, 3490-3501.
178. (c) Kaminsky, W.; Beulich, I.; Arndt-Rosenau, M. Macromol. Symp. 2001, 173, 211-225.
179. (d) Tritto, I.; Marestin, C.; Boggioni, L.; Sacchi, M. C.; Ferro, D. R. Macromolecules 2001, 34, 5770-5777.
180. (e) Ruchatz, D.; Fink, G. Macromolecules 1998, 31, 4684-4686.
181. (f) Arndt, M.; Beulich, I. Macromol. Chem. Phys. 1998, 199, 1221-1232.
182. (g) Kamisky, W.; Noll, A. Polym. Bull. 1993, 31, 175-182.
183. (a) Kumar, K. R.; Hall, C.; Penciu, A.; Drewitt, M. J.; McInenly, P. J.; Baird, M. C. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 3302-3311.
184. (b) Wang. Q.; Quyoum, R.; Gillis, D. J.; Tudoret, M.-J.; Jeremic, D.; Hunter, B. K.; Baird, M. C. Organometallics 1996, 15, 693-703.
185. (c) Barsan, F.; Baird, M. C. J. Chem. Soc., Chem. Commun. 1995, 1065-1066.
186. (d) Wang, Q.; Baird, M. C. Macromolecules 1995, 28, 8021-8027.
187. Substituents such as Me, phenyl, methoxy, etc. at the norbornyl α-position stabilize the corresponding 2-norbornyl carbocation and what is considered more likely to be a classical structure; see: (a) Laube, T. Angew. Chem., Int. Ed. Engl. 1987, 99, 580-583.
188. (b) Montgomery, L. K.; Grendze, M. P.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 4749-4750.
189. (c) Olah, G. A.; Liang, G. J. Am. Chem. Soc. 1974, 96, 195-199.
190. (d) Olah, G. A.; DeMember, J. R.; Lui, C. Y.; White, A. M. J. Am. Chem. Soc. 1969, 91, 3958-3960.
191. (e) Effects of Cl substituents in norbornane: Fry, A. J.; Farnham, W. B. J. Org. Chem. 1969, 34, 2314-2319.
192. (a) March, J. Advanced Organic Chemistry; John Wiley and Sons: New York, 1992; pp 312-326.
193. (b) Myhre, P. C.; Webb, G. G.; Yannoni, C. S. J. Am. Chem. Soc. 1990, 112, 8991-8992.
194. (c) Koch, W.; DeFrees, D. J.; Liu, B. J. Am. Chem. Soc. 1989, 111, 1527-1528.
195. (d) Olah, G. A.; Prakash, G. K. S.; Saunders: M. Acc. Chem. Res. 1983, 16, 440-448 and references therein.
196. (a) Sen, A.; Lai, T.-W.; Thomas, R. R. J. Organomet. Chem. 1988, 358, 567-588.
197. (b) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1981, 103, 4627-4629.
198. Averbuj, C.; Eisen, M. S. J. Am. Chem. Soc. 1999, 121, 8755-8759.
199. Hegedus, L. S.; Mulhern, T. A.; Asada, H. J. Am. Chem. Soc. 1986, 108, 6224-6228.
200. 2, substantial amounts (< 15% compared to the yield of propylene oligomers) of isopropyl-substituted benzene or toluene are observed due to competition between arene alkylation (reaction at the carbocationic center) and olefin oligomerization (reaction at the metal center).69
201. +) 206-212), consistent with a rapid, reversible C-H bond breaking process. See ref 56 for other examples of such processes.
202. Such a scenario is observed in Ti-benzyl complexes, where the Ti moiety is coordinated to the ipso-carbon of the phenyl group, and is confirmed by solid-state X-ray structures. For examples, see: (a) Cotton, F. A.; Murillo, C. A.; Petrukhina, M. A. J. Organomet. Chem. 1999, 573, 78-86.
203. (b) Warren, T. H.; Schrock, R. R.; Davis, W. M. Organometallics 1996, 15, 562-569.
204. (c) Bassi, I. W.; Allegra, G.; Scordamaglia, R.; Chioccola, G. J. Am. Chem. Soc. 1971, 93, 3787-3788.
205. 2 or Cp*Ti(III)Me shows that the Ti center is oriented toward the phenyl substituent with Ti-C(phenyl) contact distances in the range of 4.269-6.271 Å (for Ti(IV)) and 3.753-5.556 Å. (for Ti(III)). These distances are comparable to, and within, the range of Ti-C(phenyl) contact bond distances {3.135-5.558 Å (for Ti(IV)); 3.111-5.560 A (for Ti(III))} generated from Spartan-level calculations for the corresponding styrene-inserted Ti species (two distances from the Ti center), where 2,1-insertion of Ti-Me species into styrene occurs preferentially via multihapto coordination with the phenyl substituent during syndiospecific styrene polymerization.39.40
206. (a) O'Connor, E. J.; Kobayashi, M.; Floss, H. G.; Gladysz, J. A. J. Am. Chem. Soc. 1987, 109, 4837-4844.
207. (b) Rogers, W. N.; Baird, M. C. J. Organomet. Chem. 1979, 182, C65-C68.
208. (c) Schwartz, J.; Labinger, J. A. Angew. Chem., Int. Ed. Engl. 1976, 15, 333-340.
209. (d) Labinger, J. A.; Hart, D. W.; Seibert, W. E., III; Schwartz, J. J. Am. Chem. Soc. 1975, 97, 3851-3852.
210. (e) Periasamy, M. P.; Walborsky, H. M. J. Am. Chem. Soc. 1975, 97, 5930-5931.
211. 2 gas, respectively, with vigorous stirring. No deuteriolysis/hydrogenolysis interception products were detected; i.e., no deuterium-incorporated chloronorbornanes (resulting from deuteriolysis of the M-carbon bond) were detected by GC-MS. These results argue that such a C-H activation route is not a major competing pathway in product formation. For recent examples of similar C-H activation processes, see: (a) Hoyt, H. M.; Michael, F. E.; Bergman, R. G. J. Am. Chem. Soc. 2004, 126, 1018-1019.
212. (b) Thomas, J. C.; Peters, J. C. J. Am. Chem. Soc. 2003, 125, 8870-8888.
213. (c) Lail, M.; Arrowood, B. N.; Gunnoe, T. B. J. Am. Chem. Soc. 2003, 125, 7506-7507.
214. (d) Jia, C.; Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34, 633-639 and references therein.
215. (e) Johansson, L.; Tilset, M.; Labinger, J. A.; Bercaw, J. A. J. Am. Chem. Soc. 2000, 122, 10846-10855.