My PhD dissertation - Institut Fresnel

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106 13 C NMR (DMSO-d6): δ = 167.2, 143.3, 137.0, 133.5, 130.7, 130.5, 125.8 ppm. C14H8Br2O4 (400.02) calcd. C 42.04% H 2.02% found C 42.26% H 2.03%. Optical resolution of (±)-(PM)-6,6’-Dibromobiphenyl-2,2’-dicarboxylic acid (37): Racemic diacid (37; 8.2 g, 21 mmol) was dissolved in boiling ethanol (40 mL) and quinine (6.7 g, 21 mmol) was added. The mixture was heated for a further 30 min until it became a clear yellow solution and the temperature was slowly brought to 25 °C where crystallization occurred. The diastereoisomeric salt was filtered and recrystallized from ethanol to give colorless crystals (7.03 g). Decomposition with 10% hydrochloric acid (40 mL, 80 mmol) and the usual extraction protocol with ethyl acetate (2 × 30 mL) afforded the enriched (-)-(P)-(37) enantiomer. This protocol was repeated until optical rotatory power remained constant; colorless prisms; m.p. 234 - 236 °C; [ ] 20 α D = -7.3 (c = 1.02, ethanol); yield: 6.26 g (42%). The residue obtained after evaporation of the combined mother liquor was decomposed the same way to afford colorless prisms of the (+)-(M)-(37) enantiomer; m.p. 232 - 234 °C; [ ] 20 α D = +7.1 (c = 1.0, ethanol); yield: 5.81 g (39%). C14H8Br2O4 (400.02) calcd. C 42.04% H 2.02% found C 42.20% H 2.04%. (±)-(PM)-Dimethyl-6,6’-dibromobiphenyl-2,2’-dicarboxylate (38): (±)-(PM)-6,6’- Dibromobiphenyl-2,2’-dicarboxylic acid (37; 4.0 g, 10 mmol) was dissolved in methanol (0.10 mL) with a catalytic amount of 96% sulfuric acid and heated at 60 °C for 7 h. The mixture was then cooled down to 25 °C and crystallyzation occurred spontaneously. The solid was collected by filtration and washed with water and cold methanol to afford white prisms; m.p. 169 - 171 °C (ref. [15] m.p. 173 - 174 °C); yield: 3.77 g (88%). 1 H NMR: δ = 8.08 (dd, J = 7.8, 1.0 Hz, 2H), 7.86 (dd, J = 7.8, 1.0 Hz, 2 H), 7.37 (t, J = 7.9 Hz, 2 H), 3.66 (s, 6 H) ppm. 13 C NMR: δ = 166.0, 142.8, 136.6, 131.3, 129.7, 129.1, 125.2, 52.4 ppm. (-)-(P)-Dimethyl-6,6’-dibromobiphenyl-2,2’-dicarboxylate (P-38): Prepared following the same protocol, starting from (-)-(P)-6,6’-dibromobiphenyl-2,2’-dicarboxylic acid (37); m.p. 20 D 104 - 105 °C; [ α ] = -6.2 (c = 0.54, acetone).
107 (+)-(M)-Dimethyl-6,6’-dibromobiphenyl-2,2’-dicarboxylate (M-38): Prepared following the same protocol, starting from (+)-(M)-6,6’-dibromobiphenyl-2,2’-dicarboxylic acid (37); 20 D m.p. 103 - 105 °C; [ α ] = +5.8 (c = 0.51, acetone). C16H12Br2O4 (428.07) calcd. C 44.89% H 2.83% found C 44.65% H 2.67%. (±)-(PM)-(6,6’-Dibromobiphenyl-2,2’-diyl)dimethanol (39): Prepared following the procedure described by R. Schmid et al. [15] , starting from (±)-(PM)-dimethyl-6,6’- dibromobiphenyl-2,2’-dicarboxylate (38; 3.0 g, 7.0 mmol); colorless prisms; m.p. 130 - 132 °C (ref. [15] m.p. 134 - 136 °C); yield: 2.19 g (84%). (-)-(P)-(6,6’-Dibromobiphenyl-2,2’-diyl)dimethanol (P-39): Prepared following the same protocol, starting from (-)-(P)-dimethyl-6,6’-dibromobiphenyl-2,2’-dicarboxylate (38); m.p. [ ] 20 19 107 - 108 °C; α = -43.2 (c = 0.5, ethanol); ee > 99% (determined by F NMR analysis of D the enantiomerically pure Mosher ester derivative, in comparison with a racemic mixture of the ester). (+)-(6,6’-Dibromobiphenyl-2,2’-diyl)dimethanol (M-39): Prepared following the same protocol, starting from (+)-(M)-dimethyl-6,6’-dibromobiphenyl-2,2’-dicarboxylate (38); m.p. [ ] 20 19 105 - 107 °C; α = +41.9 (c = 0.51, ethanol). ee ≥ 98% (determined by F NMR analysis D of the enantiomerically pure Mosher ester derivative, in comparison with a racemic mixture of the ester). Preparation of Mosher ester derivative of (-)-(P)-(39) and (+)-(M)-(39): Under inert atmosphere, the diol (39, 0.17 g, 0.45 mmol) was dissolved in a mixture of carbon tetrachloride (2.0 mL) and pyridine (2.0 mL) at 25 °C and (R)-(-)-α-methoxy-α- (trifluoromethyl)-phenylacetyl chloride (0.25 mL, 0.34 g, 1.35 mmol) was added. The mixture was stirred for 20 h and the completion of the reaction was monitored by TLC. N,N-dimethylethanolamine (0.1 mL, 9.0 mg, 1.0 mmol) and the mixture was stirred for a further 30 min. Dichloromethane (5.0 mL) and 1.0 M hydrochloric acid (5.0 mL) were added and phases were decanted. The organic layer was washed with brine, dried with sodium sulfate and evaporated to dryness to afford a slightly yellow oil; yield: 347 mg (96%).
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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
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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
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 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
Page 125 and 126: 103 extraction protocol with ethyl
Page 127: 105 extracted with ethyl acetate (2
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
Page 152: O P 27i: p. 30, 80 C 9H 21OP P 26b:
Page 156: P P P O 2: p. 11, 59 3 P O O O 11:
Page 160: Nom Maurin Prénom Michaël 129 Cur
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