My PhD dissertation - Institut Fresnel

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80 C13H13NO2 (215.25) calcd. C 72.54% H 6.09% found C 71.55% H 6.03%. Ethyl bis{N-[(1S)-phenylethyl]pyrrol-2-yl}phosphinite (19): At -75 °C, butyllithium (20 mmol) in hexanes (13 mL) was added to a solution of (-)-(1S)-2-bromo- N-(1-phenylethyl)pyrrole (17; 5.0 g, 20 mmol) in toluene (20 mL). The reaction mixture was kept at - 10 °C for 20 min. Triethyl phosphite (1.7 mL, 1.7 g, 10 mmol) was then added over a period of 20 min and the solution was kept at 25 °C for 3 h. The volatiles were then evaporated to leave an orange oil. Purification by column chromatography on silica (0.16 kg) eluted with a 5 : 95 (v/v) mixture of ethyl acetate and hexanes afforded a pale yellow liquid; yield: 1.89 g (47%). 1 H NMR: δ = 7.2 (m, 6 H), 7.1 (m, 4 H), 7.01 (dd, J = 3.6, 2.1 Hz, 1 H), 6.8 m, 1H), 6.41 (symm. m, 1 H), 6.30 (dd, J = 3.0, 1.5 Hz, 1 H), 6.20 (symm. m, 1 H), 6.2 (m, 1 H), 5.92 (qd, J = 6.6, 5.1 Hz, 1 H), 5.49 (quint, J = 6.6 Hz, 1 H), 3.55 (symm. m, 2 H), 1.73 (d, J = 6.6 Hz, 3 H), 1.61 (d, J = 6.6 Hz, 3 H), 0.94 (t, J = 6.7 Hz, 3 H) ppm. 31 P NMR: δ = 143.5 ppm. MS : 416 (23%, M + +1), 105 (100%), 77 (24%).
3 The Alkaline Decomposition of Quaternary Tetraalkylphosphonium Salts 3.1 Preparation of Trialkyl Phosphines and Corresponding Trivalent Phosphorus Compounds 81 The trivalent phosphorus compounds described below are common intermediates in the preparation of most of the phosphine oxides and phosphonium salts. Since all of those compounds were highly pyrophoric, their preparation was carried out following Schlenk techniques and their purification consisted in a direct filtration/distillation step of the crude reaction mixture under inert atmosphere, using the apparatus represented below. Apparatus used for direct distillation under inert atmosphere
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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
Page 51 and 52: 31 Table 4. Mixed tertiary alkylpho
Page 53 and 54: 33 were comparable to those obtaine
Page 55 and 56: 35 led to the formation of di-tert-
Page 57 and 58: 37 depending on the alkyl substitue
Page 59 and 60: 39 4 A Novel Access to Atropisomeri
Page 61 and 62: 41 Since the homocoupling of the ha
Page 63 and 64: 43 Few other attempts to selectivel
Page 65 and 66: 45 The second phenol ether 36 was f
Page 67 and 68: 47 The enantiomeric purity was chec
Page 69 and 70: 49 A second purpose of this derivat
Page 71 and 72: 51 substrates considered. In conseq
Page 73 and 74: 53 Single-crystal X-ray analysis of
Page 75 and 76: 55 To convert atropisomer Ia into I
Page 77 and 78: 57 This finally allows one to use t
Page 79 and 80: the steric bulk and charge delocali
Page 81 and 82: 61 To check the reproducibility of
Page 83: 63 Figure 9. Full lineshape analysi
Page 86 and 87: 66 suitably substituted dilithiobip
Page 89: Experimental Part
Page 92 and 93: 70 deuterochloroform (CDCl3) unless
Page 94 and 95: 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 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
Page 125 and 126: 103 extraction protocol with ethyl
Page 127 and 128: 105 extracted with ethyl acetate (2
Page 129 and 130: 107 (+)-(M)-Dimethyl-6,6’-dibromo
Page 131 and 132: 109 (+)-(M)-2,2’-Dibromo-6,6’-b
Page 133 and 134: 111 1 H NMR: δ = 7.2 (m, 20 H), 7.
Page 135 and 136: 113 2,2’-Dilithio-6,6’-bis(meth
Page 137: References
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 146 and 147: 122 [170] B.H. Lipshutz, F. Kayser,
Page 148: 124 [212] M. Schlosser, in Organome
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O P 27i: p. 30, 80 C 9H 21OP P 26b:
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P P P O 2: p. 11, 59 3 P O O O 11:
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Nom Maurin Prénom Michaël 129 Cur
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My PhD dissertation - Institut Fresnel

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