Organozirconium complexes as catalysts for markovnikov-selective lntermolecular hydrothiolation of terminal alkynes: Scope and mechanism

Journal of the American Chemical Society

Volumn 132, Issue 30, 2010, Pages 10533-10546

  Weiss, Charles J ^a   Marks, Tobin J ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1-HEXYNE; ACTIVATION PARAMETER; ACTIVE SPECIES; ALKYNE INSERTIONS; AROMATIC THIOL; BENZYLIC; CATALYST CONCENTRATION; CATALYST RESTING STATE; DEUTERIUM LABELING; FIRST-ORDER; HYDROTHIOLATION; ISOLATED YIELD; KINETIC INVESTIGATIONS; MARKOVNIKOV SELECTIVITY; MEDIATED REACTIONS; PRECATALYSTS; PROTONOLYSIS; RADICAL INHIBITOR; RADICAL MECHANISM; REACTION MEDIUM; TEMPERATURE RANGE; TERMINAL ALKYNE; THIOLATES;

CATALYSTS; CONCENTRATION (PROCESS); DEUTERIUM; ORGANOMETALLICS; ZIRCONIUM;

ACETYLENE;

ALKYNE; DEUTERIUM; ORGANOZIRCONIUM; THIOL; UNCLASSIFIED DRUG; ZIRCONIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL REACTION; CONCENTRATION RESPONSE; HYDROTHIOLATION;

ALKYNES; CATALYSIS; ORGANOMETALLIC COMPOUNDS; SULFHYDRYL COMPOUNDS; ZIRCONIUM;

EID: 77956193621     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja103979b     Document Type: Article

References (167)

1. (a) Meng, D.; Chen, W.; Zhao, W. J. Nat, Prod, 2007, 70, 824-829.
2. (b) Zhang, Y.; Liu, S.; Che, Y.; Uu, X. J. Nat. Prod. 2007, 70, 15221525.
3. (c) Nicolaou, K. C.; Sorensen, E. J. Classics in Total Synthesis; Wiley-VHC: New York, 1996.
4. (a) Sabarre, A.; Love, J. Org. Lett. 2008, 10, 3941-3944.
5. (b) Yus, M.; GutiÈrrez, A.; Foubelo, F. Tetrafiedron 2001, 57, 4411-4422.
6. (c) Foubelo, F.; GutiÈrrez, A.; Yus, M. Tetrahedron Leu. 1999, 40, 81738176.
7. (d) Metzner, P.; Ihuillier, A., Sulfur Reagents in Organic Sytithesis; Academic Press: San Diego, 1994.
8. (e) Belen'kii, L. I. Chemistry of Organosulfur Compounds: Ellis Horwood: New York, 1990.
9. (f) de Lucchi, O.'; Pasquato, L. Tetrahedron 1988, 44, 6755-6794.
10. (a) Kloxin, C. J.; Scott, T. F.; Bowman, C. N. Macromolecules 2009, 42, 2551-2556.
11. (b) Konkolewicz, D.; Gray-Weale, A.; Perrier, S. B. J. Am. Chem, Soc. 2009, 131, 18075-18077.
12. (c) San Miguel, L.; Matzger, A. J. Macromolecules 2007,40, 9233-9237.
13. (d) Valdebenito, A.; Encinas, M. V. Polymer 2005, 46, 10658-10662.
14. (e) Roneali, J. Chem. Rev. 1992, 92, 711-738.
15. (a) Capella, L.; Montevecchi, P. C.; Navacchia, M. L. J. Org. Chem 1996, 61, 6783-6789.
16. (b) Benati, L; Capella, L.; Montevecchi, P. C.; Spagnolo, P. J. Chem. Soc, Perkin Trans. 1995, 1035-1038.
17. (c) Benati, L.; Montevecchi, P. C.; Spagnolo, P. J. Chem. Soc, Perkin Trans. 1991, 2103-2109.
18. (d) Ichinose, Y.; Wakamatsu, K.; Nozaki, K.; Birbaum, L.L.; Oshima, K.; Utimoto, K. Chem. Leu. 1987, 16, 1647-1650.
19. (e) Griesbaum, K. Angew. Chem., Int. Ed. Engl. 1970, 9, 273-287.
20. (a) Corma, A.; Gonzalez-Arellano, C; Iglesias, M.; Sanchez, F. Appl. Catal, A 2010, 375, 49-54.
21. (b) Ananikov, V. P.; Gayduk, K. A.; Orlov, N. V.; Beletskaya, I. P.; Khrastalev, V. N.; Antipin, M. Y. Chem.-Eur. J. 2010,16, 2063-2071.
22. (c) Shoai, S.; Bichler, P.; Kang, B.; Buckley, H.; Love, .J. A. Organometallics 2007, 26, 5778-5781.
23. (d) Kondoh, A.; Yorimitsu, H.; Oshima, K. Org. Lett. 2007, 9, 1383-1385.
24. (e) Fraser, L. R.; Bird, L; Wu, Q.; Cao, C.; Patrick, B. O.; Love, J. A. Organometallics 2007, 26, 5602-5611.
25. (f) Delp, S. A.; MunroLeighton, C.; Goj, L. A.; Ramirez, M. A.; Gunnoe, T. B.; Petersen, J. L.; Boyle, P. D. Inorg. Chem. 2007, 46, 2365-2367.
26. (g) Beletskaya, I. P.; Ananikov, V. P. Pure Appl. Chem. 2007, 79, 1041-1056.
27. (h) Beletskaya, I. P.; Ananikov, V. P. Eur. J. Org. Chem. 2007, 3431-3444.
28. (i) Ananikov, V. P.; Orlov, N. V.; Beletskaya, I. P.; Khrastalev, V. N.; Antipin, M.. Y.; Timofeeva, T. V. J. Am. Chem. Soc. 2007, 729, 7252-7253.
29. (j) Malyshev, D. A.; Scott, N. M.; Marion, N.; Stevens, E. D.; Ananikov, V. P.; Beletskaya, I. P.; Nolan, S. P. Organometallics 2006,25, 4462-4470.
30. (k) Ananikov, V. P.; Zalesskiy, S. S.; Orlov, N. V.; Beletskaya, I. P. Russ. Chem. Bull. 2006, 55, 2109-2113.
31. (l) Ananikov, V. P.; Orlov, N. V.; Beletskaya, I. P. Organometallics 2006, 25, 1970-1977.
32. (m) Cao, C.; Fraser, L. R.; Love, J. A. J. Am. Chem, Soc. 2005, 727,17614-17615.
33. (n) Ananikov, V. P.; Malyshev, D. A.; Beletskaya, I. P.; Aleksandrov, G. G.; Eremenko, I. L. Adv. Synth. Catal. 2005, 347,1993-2001.
34. (o) Kondo, T.; Mitsudo, T. Chem. Rev. 2000, 100, 3205-3220.
35. Misumi, Y.; Seino, H.; Mizobe, Y. J. Organomet. Chem. 2006, 691, 3157-3164.
36. (a) Hartwig, J. F. Nature 2008, 455, 314-322.
37. (b) Andrea, T.; Eisen, M. S. Chem. Soc. Rev. 2008, 37, 550-567.
38. (c) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079-3160.
39. (d) Togni, A.; Grutzmacher, H.-J. Catalytic Heterofunctionalization; Wiley-VCH: New York, 2001.
40. (a) Leitch, D. C.; Payne, P. R.; Dunbar, C. R.; Schafer, L. L. J. Am. Chem, Soc. 2009, 131, 18246-18247.
41. (b) Field, L. D.; Messerle, B. A.; Vuong, K. Q.; Turner, P. Dalton Trans. 2009, 3599-3614.
42. (c) Reznichenko, A. L.; Hampel, F.; Hultzsch, K. C. Chem.-Eur. J. 2009, 15,12819-12827.
43. (d) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795-3892.
44. (e) Munro-Leighton, C.; Delp, S. A.; Alsop, N. M.; Blue, E. D.; Gunnoe, T. B. Chem. Commun. 2008, 111-113.
45. (f) Smolensky, E.; Kapon, M.; Eisen, M. S. Organometallics 2007, 26, 4510-4527.
46. (g) Motta, A.; Fragalà, I. L.; Marks, T. L Organometallics 2006, 25, 5533-5539.
47. (h) Hong, S.; Marks, T. J. Acc. Chem Res. 2004, 37, 673-686.
48. (i) Motta, A.; Lanza, G.; Fragala, I. L.; Marks, T. L Organometallics 2004, 23, 4097-4104.
49. (j) Ryu, J.-S.i Li, G. Y.; Marks, T. L .J. Am. Chem. Soc. 2003, 125, 12584-12605.
50. (k) Ackermann, L.; Bergman, R. G.; Loy, R. N. J. Am. Chem. Soc. 2003, 125, 11956-11963.
51. (l) Ryu, L S.; Li, G. Y.; Marks, T. J. J. Am. Chem, Soc. 2003, 125, 12584-12605.
52. (m) Arredondo, V. M.; McDonald, F. E.; Marks, T. J. Organometallics 1999, 18, 19491960.
53. (n) Walsh, P. J.; Baranger, A. M.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 1708-1719.
54. (a) Perrier, A.; Comte, V.; Moïse, C.; Le Gendre, P. Chem.-Eur. J. 2009, 16, 64-67.
55. (b) Nagata, S.; Kawaguchi, S.-i.; Matsumoto, M.; Kamiya, I.; Nomoto, A.; Sonoda, M.; Ogawa, A. Tetrahedron Lett. 2007, 48, 6637-6640.
56. (c) Motta, A.; Fragalà, I. L; Marks, T. L Organometallics 2005, 24, 4995-5003.
57. (d) Sadow, A. D.; Haller, L; Fadini, L.; Togni, A. J. Am. Chem. Soc. 2004, 126, 14704-14705.
58. (e) Takaki, K.; Koshoji, G.; Komeyama, K.; Takeda, M.; Shishido, T.; Kitani, A.; Takehira, K. J. Org. Chem. 2003, 68, 6554-6565.
59. (f) Kawaoka, A. M.; Douglass, M. R.; Marks, T. J. Organometallics 2003, 22, 4630-4632.
60. (g) Douglass, M. R.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 2001, 123, 10221-10238.
61. (h) Douglass, M. R.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 1824-1825.
62. (i) Wicht, D. K.; Kourkine, I. V.; Lew, B. M.; Nthenge, J. M.; Glueck, D. S. J. Am. Chem. Soc. 1997, 779, 5039-5040.
63. (a) Dzudza, A.; Mark, T. .T. Chem.-Eur. J. 2010, 16, 3403-3422.
64. (b) Motta, A.; Fragalà, I. L.; Marks, T. J. Organometallics 2010, 29, 20042012.
65. (c) Nishina, N.; Yamamoto, Y. Tetrahedron 2009, 65, 1799-1808.
66. (d) Janini, T. E.; Rakosi, R. L.; Durr, C. B.; Bertke, J. A.; Bunge, S. D. Dalton Trans. 2009, 10601-10608.
67. (e) Dzudza, A.; Marks, T. J. Org. Lett. 2009, 11, 1523-1526.
68. (f) Cui, D.-M.; Yu, K.-R.; Zhang, C. Svnlett 2009, 7, 1103-1106.
69. (g) Seo, S.; Yu, X.; Marks, f. .T. J. Am. Chem. Soc. 2009, 131, 263-276.
70. (h) Nishina, N.; Yamamoto, Y. Tetrahedron Lett. 2008, 49, 4908-4911.
71. (i) Zhang, Z.; Widenhoefer, R. A. Org. Lett. 2008, 70, 2079-2081.
72. (j) Harkat, H.; Weibel, J.-M.; Pale, P. Tetrahedron Lett. 2007, 48, 1439-1442.
73. (k) Yu, X.; Seo, S.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 7244-7245.
74. (l) Zhang, Z.; Liu, C.; Kinder, R. E.; Han, X.; Qian, H.; Widenhoefer, R. A. J. Am. Chem. Soc. 2006, 728, 9066-9073.
75. (m) Yang, C. G.; Reich, N. W.; Shi, Z.; He, C. Org. Lett. 2005, 7, 4553-4556.
76. (n) Qian, H.; Han, X.; Widenhoefer, R. A. J. Am. Chem. Soc 2004, 126, 9536-9537.
77. Weiss, C. J.; Wobser, S. D.; Marks, T. J. J. Am. Chem. Soc. 2009, 131, 2062-2063.
78. Hegedus, L. L.; McCabe, R. W. Chemical Industries Series, Vol. 17: Catalyst Poisoning; 1984.
79. (a) Stephan, D. W.; Nadasdi, T. T. Coord. Chem, Rev. 1996, 747, 147-208.
80. (b) Krebs, B.; Henkel, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 769-788.
81. (a) Ogawa, A.; Ikeda, T.; Kimura, K.; Hirao, T. J. Ant Chem. Soc. 1999, 727, 5108-5114.
82. (b) Kuniyasu, H.; Ogawa, A.; Sato, K.; Ryu, L; Kambe, N.; Sonoda, N. J. Am. Chem. Soc. 1992, 114, 5902-5903.
83. After the insertion of alkyne into the Pd-SR bond (Scheme IB, step i), the insertion of a second alkyne into the Pd-vinyl bond occurs instead of the release of product from the metal center (Scheme IB, step ii) resulting in a diene sulfide.
84. (a) Marek, I. New Aspects of Zirconium Containing Organic Compounds; Springer: Berlin, New York, 2005.
85. (b) Marek, I. Titanium and zirconium in organic synthesis; Wiley-VCH: Weinheim, 2002.
86. (c) Hey-Hawkins, E. Chem. Rev. 1994, 94, 1661-1717.
87. (d) Poli, R. Chem. Rev. 1991, 91, 509-551.
88. (e) Cardin, D. L; Lappert, M. F.; Raston, C. L. Chemistry of Organo-Zirconium and -Hafnium Compounds; Halsted Press: New York, 1986.
89. (a) Majumder, S.; Odom, A. L. Organometallics 2008, 27, 1174-1177.
90. (b) Stubbert, B. D.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 6149-6167.
91. Carpenetti, D. W.; Kloppenburg, L.; Kupec, J. T.; Petersen, J. L. Organometallics 1996, 15, 1572-1581.
92. Wolczanski, P. T.; Bercaw, J. E. Organometallics 1982, 1, 793-799.
93. Irigoyen, A. M.; Martin, A.; Mena, M.; Palacios, F.; Yelamos, C. J. Organomet. Chem. 1995, 494, 255-259.
94. Fiandanese, V.; Marchese, G.; Naso, F.; Ronzini, L. Synthesis 1987, 1034-1036.
95. To test for temperature-dependent mechanism changes, samples were tested at constant temperature without the repeated heating/cooling and showed results consistent with those which were repeatedly heated/ cooled. Additionally, no change in the catalyst or substrates were observed as a result of the heating/cooling cycles.
96. (a) Ansyln, E. V.; Dougherty, D. A. Modem Physical Organic Chemistry; University Science Books: Sausalito, CA, 2006.
97. (b) Espenson, J. H. Chemical Kinetics and Reaction Mechanisms, 2nd ed.; McGraw-Hill: New York, 1995.
98. (c) Pilling, M. L; Seakins, P. W. Reaction Kinetics; Oxford University Press: New York, 1995.
99. Because this reaction is first-order in thiol and alkyne, excess alkyne is neccesary to drive the reaction to near completion. NMR scale reactions of 6 + 11 →12 mediated by complex 2 at 120 °C results in 50% conversion after 24 h with 2 × excess alkyne while resulting in 95% conversion with 3 × excess alkyne.
100. (a) Cotton, S. lMnthanide and Actiniae Chemistry; John Wiley & Sons, Ltd: Uppingham, Rutland, U.K., 2006.
101. (b) Li, H. X.; Ren, Z. G.; Zhang, Y.; Zhang, W. H.; Lang, J. P.; Shen, Q. J. Am. Chem. Soc. 2005, 727, 1122-1123.
102. (c) Aspinall, H. C. Chemistry ofthef-Block Elements; Taylor & Francis: Washington, DC, 2001.
103. (d) Aspinall, H. C.; Cunningham, S. A.; Maestro, P.; Macaudiere, P. Inorg. Chem. 1998, 37, 5396-5398.
104. (e) Marks, T. J. Science, 1982, 217, 989-997.
105. Fven at [thiol] > 1.2 M, when small amounts of precipitate are formed, no free CGCHj ligand is observed by NMR spectroscopy.
106. Strittmatter, R. J.; Bursten, B. E. J. Am. Chem. Soc. 1991, 113, 552-559.
107. Activation in 120 °C occurs slowly and thus sometimes requires placing the reaction in a 140 °C oil bath overnight for complete activation.
108. 2)4 (5) and benzylmercaptan (16) more slowly produces a bright orange precipitate under identical conditions.
109. Erker, G.; Froemberg, W.; Benn, R.; Mynott, R.; Angermund, K.; Krueger, C. Organometallics 1989, 8, 911-920.
110. Heyn, R. H.; Stephan, D. W. Inorg. Chem. 1995, 34, 2804-2812.
111. Fritzinger, B.; Moreels, L; Lommens, P.; Koole, R.; Hens, Z.; Martins, J. C. J. Am. Chem. Soc. 2009, 131, 3024-3032.
112. Chandra, G.; Lappert, M. F. J. Chem. Soc. A 1968, 1940-1945.
113. (a) Gregory, M. L; Braice, T. C. J. Am. Chem. Soc. 1960, 89, 2121-2127.
114. (b) Danehy, J. P.; Noel, C. J. J. Am Chem. Soc. 1960, 82, 2511-2515.
115. Additionally, 3-butyn-l-ol was tested together with 1-pentanethiol (11) and compound 1. No hydrothiolation activity was observed.
116. For thermodynamic estimates, Eyring and Arrhenius plots, and kinetic data at [Thiol] = 1.2 M, see Supporting Information.
117. Williams, L. A.; Marks, T. J. Organometallics 2009, 28, 2053-2061.
118. 1H NMR.
119. (a) Roering, A. J.; Maddox, A. F.; Elrod, L. T.; Chan, S. M.; Ghebreab, M. B.; Donovan, K. L.; Davidson, J. L; Hughes, R. P.; Shalumova, T.; MacMillan, S. N.; Tanski, J. M.; Waterman, R. Organometallics 2009, 28, 573-581.
120. (b) Hoyt, H. M.; Bergman, R. G. Angew. Chem., Int. Ed. 2007,46, 5580-5582.
121. (c) Nishiura, M.; Hou, Z. J. Mol. Catal. A: Chem. 2004,213,101-106.
122. (d) Wang, J.; Kapon, M.; Berthet, J. C.; Ephritikhine, M.; Eisen, M. S. Inorg. Chim. Acta 2002, 334, 183192.
123. (e) Dash, A. K.; Wang, J. Q.; Eisen, M. S. Organometallics 1999, 78, 4724-4741.
124. Tobisu, M.; Nakai, H.; Chatani, N. J. Org. Chem. 2009, 74, 54715475.
125. In addition to NMR, the formation of 31 and 31-D(E/Z) are also confirmed by HRMS. We are unable to support the formation of 31D2 by HRMS due to an overlapping 13C isotopic pattern.
126. 2H NMR spectra, see Supporting Information.
127. Injecting ethanethiol-d (7-d) into a completed reaction did not result in deuterium incorporation into an already formed product.
128. Coucouvanis, D.; Hadjikyriacou, A.; Lester, R.; Kanatzidis, M. G. ' Inorg. Chem. 1994, 33, 3645-3655.
129. (a) Robertson, S. D.; Slawin, A. M. Z.; Woollins, J. D. Polyhedron 2006, 25, 823-826.
130. (b) Friese, .T. C.; Krol, A.; Puke, C.; Kirschbaum, K.; Giolando, D. M. Inorg. Chem. 2000, 39, 1496-1500.
131. (c) Ashby, M. T.; Alguindigue, S. S.; Khan, M. A. Inorg. Chem, Acta 1998, 270, 227-237.
132. Howard, W. A.; Trnka, T. M.; Parkin, G. Inorg. Chem. 1995, 34, 5900-5909.
133. (a) Floquet, S. B.; Brun, S. B.; Lemonnier, J.-F.; Henry, M.; Delsuc, M.-A.; Prigent, Y.; Cadot, E.; Taulelle, F. J. Am. Chem. Soc. 2009, 131, 17254-17259.
134. (b) Li, D.; Kagan, G.; Hopson, R.; Williard, P. G. J. Am. Chem. Soc. 2009, 131, 5627-5634.
135. (c) Busetto, L.; Cassani, M, C.; Femoni, C.; Macchioni, A.; Mazzoni, R.; Zuccaccia, D. J. Organomet. Chem. 2008, 693, 2579-2591.
136. (d) Bellachioma, G.; Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D.; Macchioni, A. Coord. Chem. Rev. 2008, 252, 2224-2238.
137. (e) Pianet, I.; André, Y.; Ducasse, M.-A. S.; Tarascou, I.; Lartigue, J.-C.; Pinaud, N.I.; Fouquet, E.; Dufourc, E. L; Laguerre, M. Langmuir 2008, 24, 11027-11035.
138. (f) Macchioni, A.; Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D. Chem. Soc. Rev. 2008, 37, 479-489.
139. (a) La-Scalea, M. A.; Menezes, G. M. S.; Ferreira, E. I. THEOCHEM 2005, 730, 111-120.
140. (b) Zuccaccia, C.; Stahl, N. G.; Macchioni, A.; Chen, M.-C; Roberts, J. A.; Marks, T. J. J. Am, Chem. Soc. 2004, 126, 1448-1464.
141. (a) Sirimanne, C. T.; Yu, Z.; Heeg, M. J.; Winter, C. H. J. Organomet. Chem. 2006, 691, 2517-2527.
142. (b) Ashworth, N. J.; Conway, S. L. J.; Green, J. C; Green, M. L. H. .J. Organomet. Chem, 2000, 609, 83-88.
143. (c) Thompson, R. L.; Lee, S.; Geib, S. L; Cooper, N. L Inorg. Chem. 1993, 32, 6067-6075.
144. This diminished activity has been attributed to the greater H-S bond enthalpies; see ref 5i.
145. Fandos, R.; Lanfranchi, M.; Otero, A.; Pellinghelli, M. A.; Ruiz, M. L; Terreros, P. Organometallics 1996, 75, 4725-4730.
146. (a) Kissounko, D.; Epshteyn, A.; Fettinger, L C.; Sita, L. R. Organometallics 2006, 25, 531-535.
147. (b) O'Connor, P. E.; Morrison, D. L; Steeves, S.; Burrage, K.; Berg, D. L Organometallics 2001, 20, 1153-1160.
148. (c) Bouwkamp, M.; van Leusen, D.; Meetsma, A.; Hessen, B. Organometallics 1998, 17, 3645-3647.
149. (d) Cardin, C. J.; Cardin, D. L; Morton-Blake, D. A.; Parge, H. E.; Roy, A. Dalton Trans. 1987, 7, 1641-1645.
150. (a) Horton, A. D.; Orpen, A. G. Organometallics 1991, 10, 3910-3918.
151. (b) Burger, B. L; Thompson, M. E.; Cotter, W. D.; Bercaw, L E. J. Am. Chem. Soc. 1990, 112, 1566-1577.
152. γ-Terpinene is added in equimolar quantities to alkyne.
153. Silva, M. S.; Lara, R. G.; Marczewski, L M.; Jacob, R. G.; Lenardâo, E. L; Perm, G. Tetrahedron Lett. 2008, 49, 1927-1930.
154. (a) Shen, H.; Chan, H.-S.; Xie, Z. Organometallics 2008, 27, 11571168.
155. (b) Guerin, F.; McConville, D.H.; Vittal, J. J.; Yap, G. A. P. Organometallics 1998, 77, 5172-5177.
156. Walsh, P. J.; Hollander, F. L; Bergman, R. G. J. Organomet. Chem. 1992, 428, 13-47.
157. Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 702, 2187-2210.
158. Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 7844-7853.
159. (a) Carney, M. L; Walsh, P. L; Hollander, F. L; Bergman, R. G. Organometallics 1992, 77, 761-777.
160. (b) Carney, M. L; Walsh, P. L; Bergman, R. G. J. Am, Chem, Soc. 1990, 112, 6426-6428.
161. Hou, Z.; Breen, T. L.; Stephan, D. W. Organometallics 1993, 72,31583167.
162. Organozirconium complexes are known from the literature to cleave thiol C-S bonds; however, corresponding alkene products, indicative of this process, were not been observed by 1H NMR or GC/MS.
163. The catalytic cycle is presented here with a monomelic organozirconium complex for simplicity. See Supporting Information for a dimer catalytic cycle.
164. (a) Ugolotti, L; Kehr, G.; Fröhlich, R.; Grimme, S.; Erker, G. J. Am. Chem. Soc. 2009,131, 1996-2007.
165. (b) Albert, B. J.; Koide, K. J. Org. Chem. 2008, 73, 1093-1098.
166. (c) Rosenthal, U.; Ohff, A.; Baumann, W.; Kempe, R.; Tillack, A.; Burlakov, V. V. Angew. Chem., Int. Ed. Engl. 1994, 33, 1605-1607.
167. Protonolysis is typically rapid in reports of organozirconium- and organo-f-element-mediated hydroelementation (refs 8h,n); however, organolanthanide-catalyzed hydrophosphination (refs 9f-h) appears to have a more sluggish product protonolysis from the metal center, resulting in turnover-limiting protonolysis.