122 [170] B.H. Lipshutz, F. Kayser, Z.-P. Liu, Angew. Chem. 1994, 106, 1962 – 1964; Angew. Chem. Int. Ed. Engl. 1994, 33, 1842 – 1844. [171] B.H. Lipshutz, B. James, S. Vance, I. Carrico, Tetrahedron Lett. 1997, 38, 753 – 758. [172] A. Rajca, A. Safronov, S. Rajca, C.R. Ross, J.J. Stezowski, J. Am. Chem. Soc. 1996, 118, 7272 – 7279. [173] R. Pummerer, E. Prell, A. Rieche, Ber. Dtsch. Chem. Ges. 1926, 59, 2159 – 2161. [174] F. Leroux, M. Schlosser, Angew. Chem. 2002, 114, 4447 – 4450; Angew. Chem. Int. Ed. Engl. 2002, 41, 4272 – 4274. [175] G. Büchi, D.H. Klaubert, R.C. Shank, S.M. Weinreb, G.N. Wogan, J. Org. Chem. 1971, 36, 1143 – 1147. [176] G.M. Whitesides, J. San Filippo, C.P. Casey, E.J. Panek, J. Am. Chem. Soc. 1967, 89, 5302 – 5303. [177] G. Rauchschwalbe, M. Schlosser, Helv. Chim. Acta 1975, 58, 1094 – 1099. [178] M. Schlosser, L. Franzini, Synthesis 1998, 707 – 709. [179] J. Jacques, C. Fouquey, R. Viterbo, Tetrahedron Lett. 1971, 12, 4617 – 4620. [180] G. Delogu, D. Fabbri, M.A. Dettori, G. Casalone, A. Forni, Tetrahedron: Asymmetry 2000, 11, 1827 – 1833. [181] K. Tanaka, T. Okada, F. Toda, Angew. Chem. 1933, 105, 1266 – 1267; Angew. Chem. Int. Ed. Engl. 1993, 32, 1147 – 1148. [182] D. Cai, D.L. Hughes, T.R. Verhoeven, P.J. Reider, Tetrahedron Lett. 1995, 36, 7991 – 7994. [183] E.J. Corey, M.A. Letavic, M.C. Noe, S. Sarshar, Tetrahedron Lett. 1994, 35, 7553 – 7556. [184] M. Kawashima, A. Hirayama, Chem. Lett. 1990, 7, 2299 – 2300. [185] H.-J. Schanz, M.A. Linseis, D.G. Gilheany, Tetrahedron: Asymmetry 2003, 14, 2763 – 2769. [186] B.G. Zupancic, M. Sopcic, Synthesis 1982, 942 – 944. [187] K. Mislow, M.A.W. Glass, R.E. O'Brien, P. Rutkin, D.H. Steinberg, J. Weiss, C. Djerassi, J. Am. Chem. Soc. 1962, 84, 1455 – 1478. [188] A.W. Ingersoll, J.R. Little, J. Am. Chem. Soc. 1934, 56, 2123 – 2124. [189] M. Siegel, K. Mislow, J. Am. Chem. Soc. 1958, 80, 473 – 475. [190] W.M. Stanley, E. McMahon, R. Adams, J. Am. Chem. Soc. 1933, 55, 706 – 712. [191] J.A. Dales, D.L. Dull, H.S. Mosher, J. Org. Chem. 1969, 34, 2543 – 2549.
123 [192] W.R. Moser, C.J. Papile, D.A. Brannon, R.A. Duwell, S.J. Weininger, J. Mol. Catal. 1987, 41, 271 – 292. [193] J.D. Unruh, J.R. Christenson, J. Mol. Catal. 1982, 14, 19 – 34. [194] L.A. van der Veen, M.D.K. Boele, F.R. Bregman, P.C.J. Kamer, P.W.N.M. van Leeuwen, K. Goubitz, J. Fraanje, H. Schenk, C. Bo, J. Am. Chem. Soc. 1998, 120, 11616 – 11626. [195] T.K. Miyamoto, Y. Matsuura, K. Okude, H. Ichida, Y. Sasaki, J. Organomet. Chem. 1989, 373, C8 – C12. [196] O. Desponds, M. Schlosser, J. Organomet. Chem. 1996, 507, 257 – 261. [197] Single-crystal X-ray analysis have been performed by Dr R. Scopelliti, X-ray diffraction analysis department, EPFL, ISIC, Lausanne. [198] C.P. Casey, G.T. Whitecker, Isr. J. Chem. 1990, 30, 299 – 304; Chem. Abstr. 1991, 114, 207458y. [199] C.P. Casey, G.T. Whitecker, J. Org. Chem. 1990, 55, 1394 – 1396. [200] C.P. Casey, G.T. Whitecker, M.G. Melville, L.M. Petrovich, J.A. Gavney, D.R. Powell, J. Am. Chem. Soc. 1992, 114, 5535 – 5543. [201] K.J. Brown, M.S. Berry, K.C. Waterman, D. Lingenfelter, J.R. Murdoch, J. Am. Chem. Soc. 1984, 106, 4717 – 4723. [202] M. Kranz, H. Dietrich, W. Mahdi, G. Müller, F. Hampel, T. Clark, R. Hacker, W. Neugebauer, A.J. Kos, P.V.R. Schleyer, J. Am. Chem. Soc. 1993, 115, 4698 – 4704. [203] D.G. Lister, J.N. McDonald, N.L. Owen, in Internal Rotation and Inversion, Academic Press, London, 1978, pp. 66 – 77. [204] M. Ōki, in The Chemistry of Rotational Isomers, Springer-Verlag, Berlin, 1993, pp. 20 – 26. [205] F. Leroux, M. Maurin, N. Nicod, R. Scopelliti, Tetrahedron Lett. 2004, 45, 1899 – 1902. [206] G. Binsch, Top. Stereochem., 3, 1968, (a) pp. 98 – 99; (b) pp. 125 – 126. [207] H. Kessler, Angew. Chem. 1970, 82, 237 – 253; Angew. Chem. Int. Ed. Engl. 1970, 9, 219 – 235. [208] F. Grein, J. Phys. Chem. A 2002, 106, 3823 – 3827. [209] W.L. Meyer, R.B. Meyer, J. Am. Chem. Soc. 1963, 85, 2170 – 2171. [210] R.J. Kurland, M.B. Rubin, W.B. Wise, J. Chem. Phys. 1964, 40, 2426 – 2427. [211] Full lineshape analyses and 1 H-NMR spectra fitting were performed with gNMR 4.0.0, P. H. M. Budzelaar, Ivorysoft, Cherwell Publishing, 1997 (http://www.cherwell.com).
- Page 1:
Various Facets of Organophosphorus
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III Remerciements Je tiens à remer
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3.3.6 Relevance of the Data Assesse
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VII Literature References 115 Compo
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IX Version Abrégée Les composés
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1 Introduction 1 The present thesis
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3 research groups in the field are
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5 However, this mechanism suffers f
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7 At first, a double bromine/lithiu
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10 Although the most frequently emp
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12 The preparation of the latter ph
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protected to its dioxolane derivati
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N (S)-14 1) NBS, THF, - 75 °C 2) -
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3 Alkaline Decomposition of Phospho
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3.2 Alkyl Carbanions Stabilities in
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3.3.1 Mechanistic Discussion on the
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25 The assumption reported by these
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27 However, in the eventuality of a
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29 To prepare tertiary phosphines b
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31 Table 4. Mixed tertiary alkylpho
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33 were comparable to those obtaine
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35 led to the formation of di-tert-
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37 depending on the alkyl substitue
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39 4 A Novel Access to Atropisomeri
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41 Since the homocoupling of the ha
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43 Few other attempts to selectivel
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45 The second phenol ether 36 was f
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47 The enantiomeric purity was chec
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49 A second purpose of this derivat
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51 substrates considered. In conseq
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53 Single-crystal X-ray analysis of
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55 To convert atropisomer Ia into I
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57 This finally allows one to use t
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the steric bulk and charge delocali
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61 To check the reproducibility of
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63 Figure 9. Full lineshape analysi
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66 suitably substituted dilithiobip
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Experimental Part
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70 deuterochloroform (CDCl3) unless
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72 1 H NMR: δ = 7.32 (dddd, J = 9,
- Page 96 and 97: 1 H NMR: δ = 6.96 (s, 3 H), 6.94 (
- Page 98 and 99: 76 C21H21O9P (448.36) calcd. C 56.2
- Page 100 and 101: 78 C12H12BrN (250.13) calcd. C 57.6
- Page 102 and 103: 80 C13H13NO2 (215.25) calcd. C 72.5
- Page 104 and 105: 82 3.1.1 Dialkyl-N,N-diethylaminoph
- Page 106 and 107: 84 apparatus. The solution was adde
- Page 108 and 109: 86 Di-tert-butylisopropylphosphine
- Page 110 and 111: 88 13 C NMR: δ = 32.9 (d, J = 12 H
- Page 112 and 113: 90 13 C NMR: δ = 41.5 (d, J = 61 H
- Page 114 and 115: 31 P NMR: δ = 53.4 ppm. 92 C16H31O
- Page 116 and 117: 94 13 C NMR: δ = 40.8 (d, J = 3 Hz
- Page 118 and 119: 96 31 P NMR settings: It is known t
- Page 120 and 121: 98 Theoretical ratio: (96.1:3.9) Ex
- Page 123 and 124: 101 4 The Preparation and Racemate
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- Page 133 and 134: 111 1 H NMR: δ = 7.2 (m, 20 H), 7.
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- Page 140 and 141: 116 Conference Proceedings, Naples,
- Page 142 and 143: 118 [ 70] J. Drowart, C.E. Myers, R
- Page 144 and 145: 120 [117] S.T. Graul, R.R. Squires,
- Page 148: 124 [212] M. Schlosser, in Organome
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