Metalated 2-alkenylsulfoximines: Efficient solutions for asymmetric d3-synthons

Journal of the American Chemical Society

Volumn 118, Issue 20, 1996, Pages 4765-4777

  Reggelin, Michael ^a   Weinberger, Heinz ^a   Gerlach, Matthias ^a   Welcker, Reinhard ^a  

^a GOETHE UNIVERSITY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

SULFONAMIDE; SULFOXIDE;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS;

EID: 0029977226     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9530735     Document Type: Article

References (127)

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29. (g) In a recent paper, the Roush group introduced a new tartramide which exhibits excellent enantioselectivities with achiral aldehydes. Furthermore it performs much better with β-alkoxy-substituted chiral aldehydes than the "first generation allylic tartrales" used so far: Roush, W. R.; Grover, P. T. J. Org. Chem. 1995, 60, 3806-3813.
30. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
31. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
32. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
33. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
34. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
35. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
36. There are a number of alternative chiral boron compounds described in the literature. In a way, they represent variations on the methods introduced by the already-mentioned authors. Especially successful examples are described in the following: (a) Garcia, J.; Kim, B.; Masamune, S. J. Org. Chem. 1987, 52, 4831-4832. (b) Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892-1894. (c) Corey, E. J.; Yu, C.-M.; Kim, S. S. J. Am. Chem. Soc. 1989, 111, 5496-5498. With the diacetone glucose modified 2-alkenyl titanium reagents of M. Riediker and R. O. Duthaler, aldehydes can be allylated with enantiomeric excesses in the range of 80-90% ee: (d) Riediker, M.; Duthaler, R. O. Angew. Chem. 1989, 101, 488-490; Angew. Chem., Int. Ed. Engl. 1989, 28, 494. (e) Duthaler, R. O.; Hafner, A.; Riediker, M. Pure Appl. Chem. 1990, 62, 631-642. (f) Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. J. Am. Chem. Soc. 1992, 114, 2321-2336.
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46. The frequently used term 1,3-chirality transfer is somewhat misleading. Chirality is a property of the molecule as a whole, so strictly speaking it is not correct to assign this term to a process describing the correlated creation and removal of a stereogenic center at two atoms being separated by a third one. Nevertheless chirality transfer or transmission of chirality are well-established terms and so we will use them too as handy shortcuts for the process described above.
47. Easy accessable vinylic boronates can be homologized by the Mattesen procedure: (a) Sadhu, K. M.; Mattesen, D. S.; Hurst, G. D.; Kurosky, J. M. Organometallics, 1984, 3, 804-806. See also: (b) Matteson, D. S.; Majumdar, D. Organometallics, 1983, 2, 1529-1535. (c) Matteson, D. S.; Ray. R.; Rocks, R. R.; Tsai, D. J. Organometallics, 1983, 2, 1536-1543. (d) Brown, H. C.; Phadke, A. S.; Bhat, N. G. Tetrahedron Lett. 1993, 34, 7845-7848.
48. Easy accessable vinylic boronates can be homologized by the Mattesen procedure: (a) Sadhu, K. M.; Mattesen, D. S.; Hurst, G. D.; Kurosky, J. M. Organometallics, 1984, 3, 804-806. See also: (b) Matteson, D. S.; Majumdar, D. Organometallics, 1983, 2, 1529-1535. (c) Matteson, D. S.; Ray. R.; Rocks, R. R.; Tsai, D. J. Organometallics, 1983, 2, 1536-1543. (d) Brown, H. C.; Phadke, A. S.; Bhat, N. G. Tetrahedron Lett. 1993, 34, 7845-7848.
49. Easy accessable vinylic boronates can be homologized by the Mattesen procedure: (a) Sadhu, K. M.; Mattesen, D. S.; Hurst, G. D.; Kurosky, J. M. Organometallics, 1984, 3, 804-806. See also: (b) Matteson, D. S.; Majumdar, D. Organometallics, 1983, 2, 1529-1535. (c) Matteson, D. S.; Ray. R.; Rocks, R. R.; Tsai, D. J. Organometallics, 1983, 2, 1536-1543. (d) Brown, H. C.; Phadke, A. S.; Bhat, N. G. Tetrahedron Lett. 1993, 34, 7845-7848.
50. Easy accessable vinylic boronates can be homologized by the Mattesen procedure: (a) Sadhu, K. M.; Mattesen, D. S.; Hurst, G. D.; Kurosky, J. M. Organometallics, 1984, 3, 804-806. See also: (b) Matteson, D. S.; Majumdar, D. Organometallics, 1983, 2, 1529-1535. (c) Matteson, D. S.; Ray. R.; Rocks, R. R.; Tsai, D. J. Organometallics, 1983, 2, 1536-1543. (d) Brown, H. C.; Phadke, A. S.; Bhat, N. G. Tetrahedron Lett. 1993, 34, 7845-7848.
51. Recent examples: (a) Chen. S.-H.; Horvath, R. F.; Joglar, J.; Fisher, M. J.; Danishefsky, S. J. J. Org. Chem. 1991, 56, 5834-5845. (b) White, J. D.; Johnson. A. T. J. Org. Chem. 1990, 55, 5938-5940. (c) An unsuccessful application is described in a total synthesis of FK 506: Nakatsuka. M.; Ragan, J. A.; Sammakia, T.; Smith, D. B.; Uehling, D. E.; Schreiber, S. L. J. Am. Chem. Soc. 1990, 112, 5583-5601.
52. Recent examples: (a) Chen. S.-H.; Horvath, R. F.; Joglar, J.; Fisher, M. J.; Danishefsky, S. J. J. Org. Chem. 1991, 56, 5834-5845. (b) White, J. D.; Johnson. A. T. J. Org. Chem. 1990, 55, 5938-5940. (c) An unsuccessful application is described in a total synthesis of FK 506: Nakatsuka. M.; Ragan, J. A.; Sammakia, T.; Smith, D. B.; Uehling, D. E.; Schreiber, S. L. J. Am. Chem. Soc. 1990, 112, 5583-5601.
53. Recent examples: (a) Chen. S.-H.; Horvath, R. F.; Joglar, J.; Fisher, M. J.; Danishefsky, S. J. J. Org. Chem. 1991, 56, 5834-5845. (b) White, J. D.; Johnson. A. T. J. Org. Chem. 1990, 55, 5938-5940. (c) An unsuccessful application is described in a total synthesis of FK 506: Nakatsuka. M.; Ragan, J. A.; Sammakia, T.; Smith, D. B.; Uehling, D. E.; Schreiber, S. L. J. Am. Chem. Soc. 1990, 112, 5583-5601.
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60. (a) Hoffmann, R. W.; Landmann, B. Chem. Ber. 1986, 119, 2013-2024.
61. (b) Hoffmann, R. W.; Schlapbach, A. Tetrahedron 1992, 48, 1959-1968.
62. Reggelin, M.; Weinberger, H. Angew. Chem. 1994, 106, 489-491; Angew. Chem., Int. Ed. Engl. 1994, 33, 444-446.
63. Reggelin, M.; Weinberger, H. Angew. Chem. 1994, 106, 489-491; Angew. Chem., Int. Ed. Engl. 1994, 33, 444-446.
64. Reggelin, M.; Weinberger, H. Tetrahedron Lett. 1992, 33, 6959-6962.
65. Reggelin, M.; Welcker, R. Tetrahedron Lett. 1995, 5885-5886.
66. (a) Tamura, Y.; Minamikawa, J.; Sumoto, K.; Fujii, S.; Ikeda, M. J. Org. Chem. 1973, 38, 1239-1241.
67. (b) Review: Tamura, Y.; Minamikawa, J.; Ikeda, M. Synthesis 1977, 1-17.
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69. (a) Bickart, F. W.; Carson. F. W.; Jacobus, J.; Miller, E. G.; Mislow, K. J. Am. Chem. Soc. 1968, 90, 4869-4876.
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71. (c) Goldmann, S.; Hoffmann, R. W.; Maak, N.; Geueke, K.-J. Chem. Ber. 1980, 113, 831-844.
72. Beside this stereochemical problem this allyl sulfoxide-allyl sulfenate rearrangement hampers even the synthesis of racemic 2-alkenylsulfoximines. In the electrophilic imination of allyl phenyl sulfoxide by MSH the corresponding racemic sulfoximine was obtained with only 29% yield (Pyne, S. G.; Boche, G. Tetrahedron 1993, 49, 8449-8464).
73. (a) Reetz, M. T. Top. Curr. Chem. 1982, 106, 1-54.
74. (b) Reetz, M. T. Organotitanium Reagents in Organic Synthesis; Springer: Berlin, 1986.
75. Gais, H.-X; Erdelmeier, L; Lindner, H. J.; Vollhardt, J. Angew. Chem. 1986, 98, 914-915; Angew. Chem., Int. Ed. Engl. 1986, 25, 938.
76. Gais, H.-X; Erdelmeier, L; Lindner, H. J.; Vollhardt, J. Angew. Chem. 1986, 98, 914-915; Angew. Chem., Int. Ed. Engl. 1986, 25, 938.
77. In a very recent publication, Gais et al. used N-methylated derivatives of these titanated 2-alkenylsulfoximines for asymmetric γ-hydroxyalkylations. Moreover it was demonstrated that the obtained vinyl sulfoximines can be converted to C-silylated homoallylic alcohols by a stereoselective nickel-catalyzed rearrangement reaction: Gais, H.-J.; Müller, H.; Decker, J.; Hainz, R. Tetrahedron Lett. 1995, 7433-7436.
78. Structural details of the vinyl sulfoximine 18e (CSD-57981) have been published: Berger, B.; Bolte, M. Acta Crystallogr. 1994, C50, 1281-1282. The corresponding data for the compounds 21, 59, and 62 will be submitted to Acta Crystallogr. and are part of the supporting information.
79. Li, Y.; Houk, K. N. J. Am. Chem. Soc. 1989, 111, 1236-1240.
80. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
81. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
82. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
83. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
84. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
85. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
86. This argument holds only under the assumption that the reaction with the titanium electrophile is highly stereoselective. Although there is evidence for this to be true it is not necessarily the case. Hoppe and co-workers have observed that the stereochemical outcome of electrophilic substitution reactions involving benzylic and allylic carbanions is highly dependent on the nature of the electrophile: (a) Carstens, A.; Hoppe, D. Tetrahedron 1994, 50, 6097-6108. (b) Hoppe, D.; Carstens, A.; Krämer, T. Angew. Chem. 1990, 102, 1455-1456; Angew. Chem., Int. Ed. Engl. 1990, 29, 1424-1425. (c) Zschage, O.; Schwark, J.-R.; Krämer, T.; Hoppe, D. Tetrahedron 1992, 48, 8377-8388. (d) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 8389-8392. For studies on the stereochemistry of the electrophilic substitution reaction with stannanes see: (e) Fleming, I.; Rowley, M. Tetrahedron Lett. 1985, 3857-3858. For theoretical work in the field see: (f) Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527-537.
87. (a) Kenmink, J.; van Mierlo, C. P. M.; Scheek, R. M.; Creighton, T. E. J. Mol. Biol. 1993, 230, 312-322.
88. (b) Mierke, D. F.; Scheek, R. M.; Kessler, H. Biopolymers 1994, 34, 559-563. For the first application of ensemble DDD to obtain relative configurations from NOESY data, see: Reggelin, M.; Köck, M.; Conde-Frieboes, K.; Mierke, D. F. Angew. Chem. 1994, 106, 822-824: Angew. Chem., Int. Ed. Engl. 1994, 33, 753-755.
89. (b) Mierke, D. F.; Scheek, R. M.; Kessler, H. Biopolymers 1994, 34, 559-563. For the first application of ensemble DDD to obtain relative configurations from NOESY data, see: Reggelin, M.; Köck, M.; Conde-Frieboes, K.; Mierke, D. F. Angew. Chem. 1994, 106, 822-824: Angew. Chem., Int. Ed. Engl. 1994, 33, 753-755.
90. (b) Mierke, D. F.; Scheek, R. M.; Kessler, H. Biopolymers 1994, 34, 559-563. For the first application of ensemble DDD to obtain relative configurations from NOESY data, see: Reggelin, M.; Köck, M.; Conde-Frieboes, K.; Mierke, D. F. Angew. Chem. 1994, 106, 822-824: Angew. Chem., Int. Ed. Engl. 1994, 33, 753-755.
91. The prochirality of the double bond determines the relative topicity of the nucleophile/electrophile approach and plays therefore a major role in the control of the relative configuration at C-3 and C-4 in the addition product.
92. x are descriptors used to describe the sense of chirality (S or R) at heteroatom positions (X). This nomenclature has been introduced by D. J. Cram: Cram, D. J.; et al. J. Am. Chem. Soc. 1970, 92, 7369-7384.
93. Reggelin, M.; Weinberger, H. Manuscript in preparation.
94. (a) De Amici, M.; De Micheli, C; Molteni. G.; Pitré, D.; Carrea, G.; Riva, S.; Spezia, S.; Zetta, L. J. Org. Chem. 1991, 56, 67-72.
95. (b) Knight, D. W.; Shaw, D.; Fenton, G. Synlett 1994, 295-296. For the sake of convenience, the numbering used in the acyclic compounds is retained here.
96. (a) Brown, H. C.; Bhat, K. S.; Jadhav, P. K. J. Chem. Soc:, Perkin Trans. I 1991, 2633-2638.
97. (b) Brown, H. C.; Jadhav, P. K.; Bhat, K. S. J. Am. Chem. Soc. 1985, 107, 2564-2565.
98. Intramolecular (2-cycloalkenylmethyl)stannane-aldehyde cyclization reactions with racemic substrates have been described by S. Denmark: (a) Denmark. S. E.; Weber, E. J. J. Am. Chem. Soc. 1984, 106, 7970-7971. (b) Denmark, S. E.; Weber, E. J.; Wilson, T. M.; Willson, T. M. Tetrahedron 1989, 45, 1053-1065.
99. Intramolecular (2-cycloalkenylmethyl)stannane-aldehyde cyclization reactions with racemic substrates have been described by S. Denmark: (a) Denmark. S. E.; Weber, E. J. J. Am. Chem. Soc. 1984, 106, 7970-7971. (b) Denmark, S. E.; Weber, E. J.; Wilson, T. M.; Willson, T. M. Tetrahedron 1989, 45, 1053-1065.
100. (a) Reich, H. J.; Bowe, M. D. J. Am. Chem. Soc. 1990, 112, 8994-8995.
101. (b) Reich, H. J.; Medina, M. A.; Bowe, M. D. J. Am. Chem. Soc. 1992, 114, 11003-11004. Reich, H. I; Ringer. J. W. J Org. Chem. 1988, 53, 455-457.
102. (b) Reich, H. J.; Medina, M. A.; Bowe, M. D. J. Am. Chem. Soc. 1992, 114, 11003-11004. Reich, H. I; Ringer. J. W. J Org. Chem. 1988, 53, 455-457.
103. Reich, H. J.; Ringer, J. W. J. Org. Chem. 1988, 53, 455-457.
104. (a) Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152-161.
105. (b) Cohen T.; Guo, B.-S. Tetrahedron 1986, 42, 2803-2809.
106. Cohen, T.; Sherbine. J. P.; Matz, J. R.; Hutchins, R. R.; McKenry, B. M.; Wiley, P. R. J. Am. Chem. Soc. 1984, 106, 3245-3252.
107. Reggelin, M.; Gerlach, M. Unpublished results.
108. The configuration on the two newly created stereogenic centers has not been determined.
109. (a) Reggelin, M.; Weinberger, H. Unpublished results. Examples with racemic allylsulfoximines:
110. (b) Harmata, M.; Claassen R. J., II. Tetrahedron Lett. 1991, 32, 6497-6500.
111. (c) Pyne, S. G.; Boche, G. Tetrahedron 1993, 49, 8449-8464.
112. (a) Gais, H.-J.; Müller, H.; Bund, J.; Scommoda, M.; Brandt, J.; Raabe, G. J. Am. Chem. Soc. 1995, 117, 2453-2466.
113. (b) Bund, J.; Gais, H.-J.; Erdelmeier, I. J. Am. Chem. Soc. 1991, 113, 1442-1444.
114. An α-methylated derivative of the bicyclie ether 62 can be converted to a vinyl-substituted 2-oxabicyclo[3.3.0]octane with complete retention of the configuration at the sulfur atom: Reggelin, M.; Gerlach, M. Manuscript in preparation.
115. (a) Johnson, C. R.; Schroeck, C. W. J. Am. Chem. Soc. 1973, 95, 7418-7423.
116. (b) Johnson, C. R.; Schroeck, C. W.; Shanklin, J. R. J. Am. Chem. Soc. 1973, 95, 7424-7431.
117. (c) Johnson, C. R.; Lockard, J. P. Tetrahedron Lett. 1971, 48, 4589-4592.
118. (a) Gais, H.-J.; Müller H.; Bund, J.; Scommoda, M.; Brandt, J.; Raabe, G. J. Am. Chem. Soc. 1995, 117, 2453-2466.
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120. (a) Gais, H.-J.; Erdelmeier, I. J. Am. Chem. Soc. 1989, 111, 1125-1126.
121. (b) Gais, H.-J.; Müller, H.; Decker, J.; Hainz, R. Tetrahedron Lett. 1995, 7433-7436.
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123. (a) Johnson, C. R.; Zeller, J. R. J. Am. Chem. Soc. 1982, 104, 4021.
124. (b) Poupart, M-A.; Paquette, L. A. Tetrahedron Lett. 1988, 29, 269-272.
125. Prepared by methylation of the C-epimeric sulfinamide described in ref 16.
126. Vedejs, E. J. Org. Chem. 1978, 43, 188-190.
127. Cope. A. C.; Estes, L. L. J. Am. Chem. Soc. 1950, 72, 1128-1132.