Highly selective palladium catalyzed kinetic resolution and enantioselective substitution of racemic allylic carbonates with sulfur nucleophiles: Asymmetric synthesis of allylic sulfides, allylic sulfones, and allylic alcohols

Chemistry - A European Journal

Volumn 9, Issue 17, 2003, Pages 4202-4221

  Gais, Hans Joachim ^a   Jagusch, Thomas ^a   Spalthoff, Nicole ^a   Gerhards, Frank ^a   Frank, Michael ^a   Raabe, Gerhard ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

Allylic compounds; Asymmetric catalysis; Asymmetric synthesis; Kinetic resolution; Palladium

Indexed keywords

ALLYL RESINS; CATALYSIS; NEGATIVE IONS; PALLADIUM; SUBSTRATES; SYNTHESIS (CHEMICAL);

NUCLEOPHILES;

CARBONATES;

ALLYL ALCOHOL; ALLYL COMPOUND; ALLYL SULFIDE; CARBONIC ACID DERIVATIVE; PALLADIUM; SULFONE DERIVATIVE;

ARTICLE; ASYMMETRIC SYNTHESIS; CATALYSIS; CATALYST; CHEMICAL REACTION; ENANTIOMER; ENANTIOSELECTIVITY; REACTION ANALYSIS; SUBSTITUTION REACTION;

ALCOHOLS; ALLYL COMPOUNDS; CARBONATES; CATALYSIS; CRYSTALLOGRAPHY, X-RAY; KINETICS; LITHIUM; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PALLADIUM; STEREOISOMERISM; SULFIDES; SULFINIC ACIDS; SULFONES;

EID: 0141649362     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200204657     Document Type: Article

References (199)

1. a) H. B. Kagan, J. C. Fiaud, Top. Stereochem. 1988, 18, 249;
2. b) C. J. Sih, S.-H. Wu, Top. Stereochem. 1989,19, 63;
3. c) J. Jacques, A. Collet, S. H. Wilen, Enantiomers, Racemates, and Resolutions, Krieger, Malabar, 1991;
4. d) Chirality in Industry (Eds.: A. N. Collins, G. N. Sheldrake, J. Crosby), Wiley, New York, 1992;
5. e) R. A. Sheldon, Chirotechnology, Marcel Dekker, New York, 1993;
6. f) E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994;
7. g) R. S. Ward, Tetrahedron: Asymmetry 1995, 6, 1475;
8. h) A. H. Hoveyda, M. T. Didiuk, Curr. Org. Chem. 1998, 2, 489;
9. i) A. Collet, Enantiomer 1999, 4, 157;
10. j) T. O. Lukas, C. Girard, D. R. Fenwick, H. B. Kagan, J. Am. Chem. Soc. 1999, 121, 9299;
11. k) D. W. Johnson, Jr., D. A. Singleton, J. Am. Chem. Soc. 1999, 121, 9307;
12. l) D. Wistuba, V. J. Schurig, J. Chromatogr. A 2000, 875, 255;
13. m) G. R. Cook, Curr. Org. Chem. 2000, 4, 869;
14. n) J. M. Keith, J. F. Larrow, E. N. Jacobsen, Adv. Synth. Catal. 2001, 343, 5;
15. o) D. G. Blackmond, J. Am. Chem. Soc. 2001, 123, 545;
16. p) H. B. Kagan, Tetrahedron 2001, 57, 2449;
17. q) H.-J. Gais, F. Theil in Enzyme Catalysis in Organic Synthesis, Vol. II (Eds.: K. Drauz, H. Waldmann), Wiley-VCH, Weinheim, 2002, p. 335;
18. r) A. Bommarius in Enzyme Catalysis in Organic Synthesis, Vol. II (Eds.: K. Drauz, H. Waldmann), Wiley-VCH, Weinheim, 2002, p. 741.
19. While resolution by classical methods and by chromatography generally gives access to both enantiomers, kinetic resolution yields one enantiomer of the starting material and a product which may or may not be readily convertible to the other enantiomer of the starting material. Illustrative examples for the later aspect are the hydrolase catalyzed resolution of the acetates of racemic alcohols giving a mixture of the alcohol and the acetate[1q] and the transition metal catalyzed oxidative resolution of benzylic alcohols yielding a mixture of the alcohol and the ketone[1n].
20. a) J. Tsuji, Palladium Reagents and Catalysts, Wiley, New York, 1997;
21. b) S. J. Sesay, J. M. J. Williams, Adv. Asymmetric Synth. 1998, 3, 235;
22. c) A. Heumann in Transition Metals for Organic Synthesis, Vol. I (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim, 1998, p. 251;
23. d) B. M. Trost, C. Lee in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), Wiley-VCH, Weinheim, 2000;
24. e) G. Helmchen, A. Pfaltz, Acc. Chem. Res. 2000, 33, 336;
25. f) G. Helmchen, J. Organomet. Chem. 1999, 576, 203;
26. g) M. Moreno-Mañas, R. Pleixats in Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 2 (Eds.: E. Negishi, A de Meijere), Wiley, New York, 2002, p. 1707;
27. h) L. Acemoglu, J. M. J Williams in Handbook of Organopalladium Chemistry, Vol. 2 (Eds.: E. Negishi, A. de Meijere), Wiley, New York, 2002, p. 1945.
28. a) Although Scheme 1 shows only symmetrically substituted acyclic substrates, it is in principle also valid for symmetrically substituted cyclic and for unsymmetrically substituted substrates. Scheme 1 is a simplified representation of the palladium-catalyzed allylic substitution because of the omission of the syn, syn- and anti, syn-isomerism of the π-allyl complexes as well as of the formation of contact ion pairs and the coordination of the leaving group or the nucleophile to the palladium atom with formation of neutral complexes;
29. b) symmetrically disubstituted allylic substrates are the most popular ones in palladium catalyzed allylic substitution because of the avoidance of otherwise difficult to control regioselectivity problems which generally arise with monosubstituted and unsymmetrically disubstituted substrates;
30. 2 symmetry (see text).
31. a) P. B. Mackenzie, J. Whelan, B. Bosnich, J. Am. Chem. Soc. 1985, 107, 2046;
32. b) K. L. Granberg, J. E. Bäckvall, J. Am. Chem. Soc. 1992, 114, 6858.
33. T. Hayashi, A. Yamamoto, I. Yoshihiko, J. Chem. Soc. Chem. Commun. 1986, 1090.
34. H.-J. Gais, H. Eichelmann, N. Spalthoff, F. Gerhards, M. Frank, G. Raabe, Tetrahedron: Asymmetry 1998, 9, 235.
35. a) A. Pfaltz, Acta Chem. Scand. Ser. B 1996, 50, 189;
36. b) G. Helmchen, S. Kudis, P. Sennhenn, H. Steinhagen, Pure Appl. Chem. 1997, 69, 513;
37. c) J. M. J. Williams, Synlett 1996, 705.
38. M. Frank, H.-J. Gais, Tetrahedron: Asymmetry 1998, 9, 3353.
39. B. M. Trost, D. L. Van Vranken, C. Bingel, J. Am. Chem. Soc. 1992, 114, 9327.
40. a) M. Bourghida, M. Widhalm, Tetrahedron: Asymmetry 1998, 9, 1073;
41. b) H. Brunner, I. Deml, W. Dirnberger, K.-P. Ittner, W. Reißer, M. Zimmermann, Eur. J. Inorg. Chem. 1999, 51;
42. c) S. Ramdeehul, P. Dierkes, R. Aguado, P. C. J. Kamer, P. W. N. M. van Leeuwen, J. A. Osborn, Angew. Chem. 1998, 110, 3302; Angew. Chem. Int. Ed. 1998, 37, 3118;
43. c) S. Ramdeehul, P. Dierkes, R. Aguado, P. C. J. Kamer, P. W. N. M. van Leeuwen, J. A. Osborn, Angew. Chem. 1998, 110, 3302; Angew. Chem. Int. Ed. 1998, 37, 3118;
44. d) G. C. Lloyd-Jones, S. C. Stephen, Chem. Commun. 1998, 2321;
45. e) B. M. Trost, E. J. Hembre, Tetrahedron Lett. 1999, 40, 219;
46. f) B. M. Trost, F. D. Toste, J. Am. Chem. Soc. 1999, 121, 3543;
47. g) T. Nishimata, K. Yamaguchi, M. Mori, Tetrahedron Lett. 1999, 40, 5713;
48. h) M. T. Reetz, S. Sostmann, J. Organomet. Chem. 2000, 603, 105;
49. i) J. M. Longmire, B. Wang, X. Zhang, Tetrahedron Lett. 2000, 41, 5435;
50. j) T. Okauchi, K. Fujita, T. Ohtagura, S. Ohshima, T. Minami, Tetrahedron: Asymmetry 2000, 11, 1397;
51. k) B. M. Trost, J. Dudash, Jr., E. J. Hembre, Chem. Eur. J. 2001, 7, 16191;
52. l) S. R. Gilbertson, P. Lan, Org. Lett. 2001, 3, 2237;
53. m) B. Dominguez, N. S. Hodnett, G. C. Lloyd-Jones, Angew. Chem. 2001, 113, 4419;Angew. Chem. Int. Ed. 2001, 40, 4289.
54. m) B. Dominguez, N. S. Hodnett, G. C. Lloyd-Jones, Angew. Chem. 2001, 113, 4419;Angew. Chem. Int. Ed. 2001, 40, 4289.
55. a) R. A. Johnson, K. B. Sharpless in Comprehensive Organic Synthesis, Vol. 7 (Ed.: B. M. Trost), Pergamon, Oxford, 1991, p. 389;
56. b) R. F. Heck, Palladium Reagents in Organic Synthesis, Academic, London, 1985, Chapter 5;
57. c) R. A. Johnson, K. B. Sharpless in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, Weinheim, 1993, Chapter 4.
58. For selected examples of the asymmetric synthesis of allylic alcohols, see: a) S. K. Bertilsson, M. J. Södergren, P. G. Andersson, J. Org. Chem. 2002, 67, 1567;
59. b) M. B. Andrus, Z. Zhou, J. Am. Chem. Soc. 2002, 124, 8806;
60. c) Y. Kohmura, T. Katsuki, Tetrahedron Lett. 2000, 41, 3941;
61. d) E. J. Corey, C. J. Helal, Angew. Chem. 1998, 110, 2092; Angew. Chem. Int. Ed. 1998, 37, 1986;
62. d) E. J. Corey, C. J. Helal, Angew. Chem. 1998, 110, 2092; Angew. Chem. Int. Ed. 1998, 37, 1986;
63. e) J. B. Alexander, D. S. La, D. R. Cefalo, A. H. Hoveyda, R. R. Schrock, J. Am. Chem. Soc. 1998, 120, 4041;
64. f) M. Asami, T. Ishizaki, S. Inoue, Tetrahedron: Asymmetry 1994, 5, 793;
65. g) H. C. Brown, K. S. Bhat, P. K. Jadhav, J. Chem. Soc. Perkin Trans. 1 1991, 2633;
66. h) R. Noyori, I. Tomino, M. Nishizawa, J. Am. Chem. Soc. 1979, 101, 5843.
67. a) V. S. Martin, S. S. Woodard, T. Katsuki, Y. Yamada, M. Ikeda, K. B. Sharpless, J. Am. Chem. Soc. 1981, 103, 6237;
68. b) S. S. Woodward, M. G. Finn, K. B. Sharpless, J. Am. Chem. Soc. 1991, 113, 106.
69. a) J. W. Faller, M. Tokunaga, Tetrahedron Lett. 1993, 34, 7359;
70. b) M. S. Visser, J. P. A. Harrity, A. H. Hoveyda, J. Am. Chem. Soc. 1996, 118, 3779;
71. c) S. Hashiguchi, A. Fujii, K.-J. Haack, K. Matsumura, T. Ikariya, R. Noyori, Angew. Chem. 1997, 109, 300; Angew. Chem. Int. Ed. Engl. 1997, 36, 288;
72. c) S. Hashiguchi, A. Fujii, K.-J. Haack, K. Matsumura, T. Ikariya, R. Noyori, Angew. Chem. 1997, 109, 300; Angew. Chem. Int. Ed. Engl. 1997, 36, 288;
73. d) S. R. Araneo, E. Cesarotti, D. Berta, Appl. Organomet. Chem. 2000, 14, 735.
74. a) A. K. Gupta, R. J. Kazlauskas, Tetrahedron: Asymmetry 1993, 4, 879;
75. b) T. Fukazawa, Y. Shimoji, T. Hashimoto, Tetrahedron: Asymmetry 1996, 7, 1649;
76. c) W. Adam, C. Mock-Knoblauch, C. R. Saha-Möller, Tetrahedron: Asymmetry 1997, 8, 1441;
77. d) H. Bärmann, Angew. Chem. 1996, 108, 1825; Angew. Chem. Int. Ed. Engl. 1996, 35, 1678.
78. d) H. Bärmann, Angew. Chem. 1996, 108, 1825; Angew. Chem. Int. Ed. Engl. 1996, 35, 1678.
79. a) J. M. J. Williams, J. V. Allen, Tetrahedron Lett. 1996, 37, 1859;
80. b) Y. K. Choi, J. H. Suh, D. Lee, I. T. Lim, J. Y. Jung, M.-J. Kim, J. Org. Chem. 1999, 64, 8423.
81. a) M. Frohn, X. Zhou, J.-R. Zhang, Y. Tang, Y. Shi, J. Am. Chem. Soc. 1999, 121, 7718;
82. b) S. Bellemin-Laponnaz, J. Tweddell, J. C. Ruble, F. M. Breitling, G. C. Fu, Chem. Commun. 2000, 1009;
83. c) E. Vedejs, J. MacKay, A. Org. Lett. 2001, 3, 535.
84. a) R. C. Hartley, S. Warren, I. C. Richards, Tetrahedron Lett. 1992, 33, 8155; R. C. Hartley, S. Warren, I. C. Richards, J. Chem. Soc. Perkin Trans. 1 1994, 507;
85. a) R. C. Hartley, S. Warren, I. C. Richards, Tetrahedron Lett. 1992, 33, 8155; R. C. Hartley, S. Warren, I. C. Richards, J. Chem. Soc. Perkin Trans. 1 1994, 507;
86. b) O. Meyer, P. C. Cagle, K. Weickhardt, D. Vichard, J. A. Gladysz, Pure Appl. Chem. 1996, 68, 79;
87. c) D. S. Carter, D. L. Van Vranken, Tetrahedron Lett. 1999, 40, 1617;
88. d) V. K. Aggarwal, M. Ferrara, R. Hainz, S. E. Spey, Tetrahedron Lett. 1999, 40, 8923;
89. e) D. W. McMillen, N. Varga, B. A. Reed, C. King, J. Org. Chem. 2000, 65, 2532;
90. f) T. Bach, C. Körber, J. Org. Chem. 2000, 65, 2358;
91. g) S. Kitagaki, Y. Yanamoto, H. Okubo, M. Makajima, S. Hashimoto, Heterocycles 2001, 54, 623;
92. h) L. Brandsma, P. J. W. Schuijl, D. Schuijl-Laros, J. Meijer, H. E. Wijers, Int. J. Sulfur Chem. Part B 1971, 6, 85;
93. i) P. Metzner, Synthesis 1992, 1185;
94. j) R. C. Schnur, M. L. Corman, J. Org. Chem. 1994, 59, 2581;
95. k) B. Ernst, J. Gonda, R. Jeschke, U. Nubbemeyer, R. Oehrlein, D. Bellus, Helv. Chim. Acta 1997, 80, 876;
96. l) S. He, R. A. Kozmin, V. H. Rawal, J. Am. Chem. Soc. 2000, 122, 190.
97. a) M. Julia, A. Guy-Rouault, Bull. Soc. Chim. Fr. 1967, 1411;
98. b) M. Julia, D. Arnold, Bull. Soc. Chim. Fr. 1973, 743;
99. c) B. Lythgoe, I. Waterhouse, J. Chem. Soc. Perkin Trans. 1 1979, 2429;
100. d) B. M. Trost, N. R. Schmuff, M. J. Miller, J. Am. Chem. Soc. 1980, 102, 5979;
101. e) S. E. Denmark, M. A. Harmata, J. Am. Chem. Soc. 1982, 104, 4972;
102. f) T. Mandai, T. Yanagi, K. Araki, Y. Morisaki, M. Kawada, J. Otera, J. Am. Chem. Soc. 1984, 106, 3670;
103. g) B. M. Trost, M. Reza Ghadiri, J. Am. Chem. Soc. 1984, 106, 7260;
104. h) J. A. Marshall, R. C. Andrews, J. Org. Chem. 1985, 50, 1602;
105. i) S. D. A. Street, C. Yeates, P. Kocienski, S. F. Campbell, J. Chem. Soc. Chem. Commun. 1985, 1386;
106. j) T. Cuvigny, M. Julia, C. Rolando, J. Organomet. Chem. 1985, 285, 395;
107. k) G. Consiglio, O. Piccolo, L. Roncetti, F. Morandini, Tetrahedron 1986, 42, 2043;
108. l) T. Cuvigny, C. Herve du Penhoat, M. Julia, Tetrahedron 1986, 42, 5329;
109. m) B. M. Trost, C. A. Merlic, J. Am. Chem. Soc. 1988, 110, 5216;
110. n) H.-J. Gais, W. A. Ball, J. Bund, Tetrahedron Lett. 1988, 29, 781;
111. o) B. M. Trost, C. A. Merlic, J. Org. Chem. 1990, 55, 1127;
112. p) K. Tsuboyama, K. Takeda, K. Torii, H. Ogura, Chem. Pharm. Bull. 1990, 38, 2357;
113. q) A. Padwa, S. H. Watterson, Z. Ni, J. Org. Chem. 1994, 59, 3256;
114. r) Z. Jin, P. L. Fuchs, Tetrahedron Lett. 1996, 37, 5253;
115. s) V. Caló, A. Nacci, V. Fiandanese, Tetrahedron 1996, 52, 10799.
116. For reviews, see: a) J.-F. Biellman, J.-B. Ducep, Org. React. 1982, 27, 1;
117. b) S. Oae, Y. Uchida in The Chemistry of Sulfones and Sulfoxides (Eds.: S. Patai, Z. Rappoport, C. J. M. Stirling), Wiley, New York, 1988, p. 583;
118. c) K. Ogura in Comprehensive Organic Synthesis, Vol. 1 (Ed.: S. L. Schreiber), Pergamon, Oxford, 1991, p. 505;
119. d) A. Krief in Comprehensive Organic Synthesis, Vol. 3 (Ed.: G. Pattenden), Pergamon, Oxford, 1991, p. 85;
120. e) Y. Yamamoto in Comprehensive Organic Synthesis, Vol. 3 (Ed.: C. H. Heathcock), Pergamon, Oxford, 1991, p. 55;
121. f) N. S. Simpkins, Sulphones in Organic Synthesis, Pergamon, Oxford, 1993;
122. g) M. Braun in Stereoselective Synthesis (Houben-Weyl), Vol. E21b (Eds.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, p. 1713;
123. h) S. Pyne in Stereoselective Synthesis (Houben-Weyl), Vol. E21b (Eds.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, p. 2068.
124. H.-J. Gais, N. Spalthoff, T. Jagusch, M. Frank, G. Raabe, Tetrahedron Lett. 2000, 41, 3809.
125. a) B. M. Trost, M. G. Organ, G. A. O'Doherty, J. Am. Chem. Soc. 1995, 117, 9662;
126. b) B. M. Trost, M. J. Krische, R. Radinov, G. Zanoni, J. Am. Chem. Soc. 1996, 118, 6297;
127. c) B. M. Trost, A. C. Krueger, R. C. Bunt, J. Zambrano, J. Am. Chem. Soc. 1996, 118, 6520.
128. H. Eichelmann, H.-J. Gais, Tetrahedron: Asymmetry 1995, 6, 643.
129. a) H.-J. Gais, G. Hellmann, J. Am. Chem. Soc. 1992, 114, 4439;
130. b) L. Glendenning, L. D. Field, R. K. Haynes, Bull. Chem. Soc. Jpn. 1995, 68, 2739;
131. c) M. Piffl, J. Weston, E. Anders, Eur. J. Org. Chem. 2000, 2851;
132. d) H.-J. Gais, M. van Gumpel, M. Schleusner, G. Raabe, J. Runsink, C. Venneeren, Eur. J. Org. Chem. 2001, 4275;
133. e) F. Marr, R. Fröhlich, B. Wibbeling, C. Diedrich, D. Hoppe, Eur. J. Org. Chem. 2002, 2970.
134. a) A. Singhal, V. K. Jain, J. Organomet. Chem. 1995, 494, 75;
135. b) Y. Miyauchi, S. Watanabe, H. Kuniyasu, H. Kurosawa, Organometallics 1995, 14, 5450;
136. c) J. Ruiz, J. Giner, V. Rodriguez, G. López, J. Casabó, E. Molins, C. Miravitlles, Polyhedron 2000, 19, 1627;
137. d) C. Savarin, J. Srogl, L. S. Liebeskind, Org. Lett. 2000, 2, 3229;
138. e) R. Redón, H. Torrens, Z. wang, D. Morales-Morales, J. Organomet. Chem. 2002, 654, 16.
139. a) B. M. Trost, T. S. Scanlan, Tetrahedron Lett. 1986, 27, 4141;
140. b) R. Auburn, J. Whelan, B. Bosnich, Organometallics 1986, 5, 1533;
141. c) C. Goux, P. Lhoste, D. Sinou, Tetrahedron Lett. 1992, 33, 8099;
142. d) J. P. Genêt, E. Blart, M. Savignac, S. Lemeune, S. Lemaire-Audore, J. M. Bernard, Synlett 1993, 680;
143. e) M. Moreno-Mafias, R. Pleixats, M. Villarroya, Tetrahedron 1993, 49, 1457;
144. f) Y. Arredondo, M. Moreno-Mañas, R. Pleixats, M. Villarroya, Tetrahedron 1993, 49, 1465;
145. g) C. Goux, P. Lhoste, D. Sinou, Tetrahedron 1994, 35, 10321.
146. a) A. Böhme, H.-J. Gais, Tetrahedron: Asymmetry 1999, 10, 2511;
147. b) H.-J. Gais, A. Böhme, J. Org. Chem. 2002, 67, 1153.
148. D. Sinou, S. Divekar, M. Safi, M. Soufiaoui, Sulf Lett. 1999, 22, 125.
149. H.-J. Gais, B. Lüssem, unpublished results.
150. For preliminary communications of parts of this work, see ref [9, 22].
151. a) H. W. Pinnick, M. A. Reynolds, J. Org. Chem. 1979, 44, 160;
152. b) H. Eichelmann, Ph.D. thesis, RWTH Aachen (Germany), 1997.
153. T. Ukai, H. Kawazura, Y. Ishii, J. J. Bonnet, J. A. Ibers, J. Organomet. Chem. 1974, 65, 253.
154. K. Hiroi, K. Makino, Chem. Pharm. Bull. 1988, 36, 1744.
155. H.-J. Gais, T. Jagusch, O. Bondarev, unpublished results.
156. G. B. Barlin, M. D. Fenn, Heterocycles 1986, 24, 1301.
157. W. T. Dent, R. Long, A. J. Wilkinson, J. Chem. Soc. 1964, 1585.
158. a) B. Akermark, S. Hansson, A. Vitagliano, J. Am. Chem. Soc. 1990, 112, 2642;
159. b) M. Skögren, S. Hansson, P.-O. Norrby, B. Akermark, M. E. Cucciolito, A. Vitagliano, Organometallics 1992, 11, 3954;
160. c) U. Kazmaier, F. L. Zumpe, Angew. Chem. 2000, 112, 805; Angew. Chem. Int. Ed. 2000, 39, 802;
161. c) U. Kazmaier, F. L. Zumpe, Angew. Chem. 2000, 112, 805; Angew. Chem. Int. Ed. 2000, 39, 802;
162. d) P. Corradini, G. Maglio, A. Musco, G. Paiaro, J. Chem. Soc. Chem. Commun. 1966, 618.
163. a) M. Wisniewski, Pol. J. Chem. 1989, 63, 3;
164. b) M. R. Crampton in The Chemistry of the Thiol Group (Ed.: S. Patai), Wiley, London, 1974, p. 396;
165. c) J. Katritsky, J. Chem. Soc. 1958, 3610;
166. d) E. M. Arnett, L. E. Small, J. Am. Chem. Soc. 1977, 99, 808;
167. e) W. Behrendt, G. Gattow, Z. Anorg. Allg. Chem. 1973, 398, 198.
168. a) B. M. Trost, R. C. Bunt, J. Am. Chem. Soc. 1996, 118, 235;
169. b) G. C. Lloyd-Jones, S. C. Stephen, Chem. Eur. J. 1998, 4, 2539;
170. c) C. P. Butts, J. Crosby, G. C. Lloyd-Jones, S. C. Stephen, Chem. Commun. 1999, 1707;
171. d) I. J. S. Fairlamb, G. C. Lloyd-Jones, Chem. Commun. 2000, 2447;
172. e) B. M. Trost, J.-P. Surivet, J. Am. Chem. Soc. 2000, 122, 6291;
173. f) I. J. S. Fairlamb, G. C. Lloyd Jones, S. C. Stephen, Chem. Eur. J. 2002, 8, 4443;
174. g) G. C. Lloyd-Jones, personal communication, 28. 6. 2002.
175. h) B. M. Trost, X. Ariza, J. Am. Chem. Soc. 1999, 121, 10727.
176. a) Modern Practice of Gas Chromatography (Ed.: R. L. Grob), Wiley, New York, 1995;
177. b) W. A. Bonner, J. Chromatogr. Sci. 1973, 11, 101;
178. c) H. Frank, G. J. Nicholson, E. Bayer, J. Chromatogr. 1978, 167, 187;
179. d) V. Schurig in Asymmetric Synthesis, Vol. 1 (Ed.: J. D. Morrison), Academic, New York, 1983, p. 59.
180. a) In enzymatic kinetic resolution often the designation E (enantiomeric ratio) is used instead of S[1b, q];
181. b) generally the selectivity factor S for a kinetic resolution obeying first-order kinetics in regard to the substrate can also be calculated by using equations, which contain either the conversion of the substrate and the enantiomeric excess of the product or the ee of the product and the ee of the substrate.[1a, b] However, since in palladium-catalyzed kinetic resolution of allylic substrates the ee value of the product and of the remaining substrate are determined at different stages of the overall catalytic cycles leading to the product, these equations can not be used. Furthermore, because of this difference measurement of the conversion through measurements of the ee of the product and the ee of the substrate is not possible.
182. For a Java applet, KinRes, for the calculation of S according to Equation (3), see: http://www.ch.cam.ac.uk/MMRG/kinres/
183. J. M. Goodman, A.-K. Köhler, S. C. M. Alderton, Tetrahedron Lett. 1999, 40, 8715.
184. For insightful discussions of the possible pitfalls of a description of a kinetic resolution by the selectivity factor S, see: ref. [1n, o, 44].
185. a) For example, calculation of S for c = 48 ± 0.5% and ee = 89 ± 0.5% gives values ranging from 95 to 564;
186. b) for examples of irregular changes of S in palladium catalyzed kinetic resolution of allylic substrates, see: ref. [11c, h];
187. c) for examples of an increase and a decrease of S with conversion in palladium catalyzed kinetic resolution of allylic substrates, see: ref. [11m] and [11i], respectively.
188. A. A. Frost, R. G. Pearson, Kinetics and Mechanism, Wiley, New York, 1961, p. 14.
189. F. Frank, Ph.D. thesis, RWTH Aachen, 1999.
190. B. Morgan, A. C. Oehlschlager, T. M. Stokes, J. Org. Chem. 1992, 57, 3231.
191. a) M. J. Södergren, P. G. Andersson, J. Am. Chem. Soc. 1998, 120, 10760;
192. b) R. K. Hill, R. Soman, S. Sawada, J. Org. Chem. 1972, 37, 3737.
193. B. Lüssem, H.-J. Gais, unpublished results.
194. For a highly selective palladium-catalyzed deracemization of rac-1a-c, rac-3aa and rac-3ba in the presence of BPA with formation of 9a-c, 10a and 10b, respectively, see: B. J. Liissem, H.-J. Gais, J. Am. Chem. Soc. 2003, 125, 6066.
195. G. Koch, G. C. Lloyd-Jones, O. Loiseleur, A. Pfaltz, Recl. Trav. Chim. Pays-Bas 1995, 114, 206.
196. a) S. R. Hall, G. S. D. King, J. M. Stewart, XTAL 3.4 User's Manual, Universities of Western Australia, Leuven and Maryland, Lamb, Perth, 1995;
197. b) E. Keller SCHAKAL 92, Universität Freiburg (Germany), 1992;
198. c) CCDC-142405 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam. ac.uk);
199. d) H. D. Flack, Acta Crystallogr. Sect. A 1983, 39, 876.