My PhD dissertation - Institut Fresnel

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108 (R)-(-)-MTPA ester from (-)-(P)-(39): prepared as described above; yield: 347 mg (96%). 1 H NMR: δ = 7.6 (m, 3 H), 7.4 - 7.2 (m, 13 H), 5.04 (d, J = 13.5 Hz, 2 H), 4.80 (d, J = 13.5 Hz, 2 H), 3.50 (s, 6 H) ppm. 19 F NMR: δ = -71.5 ppm. (R)-(-)-MTPA ester from (+)-(M)-(39): Prepared as described above; yield: 340 mg (94%). 1 H NMR: δ = 7.6 (m, 3 H), 7.4 - 7.2 (m, 13 H), 4.95 (d, J = 13.3 Hz, 2 H), 4.80 (d, J = 13.3 Hz, 2 H), 3.45 (s, 6 H) ppm. 19 F NMR: δ = -71.9 ppm. (±)-(PM)-2,2’-Dibromo-6,6’-bis(methoxymethyl)biphenyl (41): At 0 °C, a solution of (±)-(PM)-(6,6’-dibromobiphenyl-2,2’-diyl)dimethanol (39; 2.5 g, 6.7 mmol) in tetrahydrofuran (15 mL) was added to a suspension of sodium hydride (0.41 g, 17 mmol) in tetrahydrofuran (5.0 mL). After the end of hydrogen emission, iodomethane (0.5 mL, 1.1 g, 8.0 mmol) was added at 25 °C to the reddish suspension which slowly faded to beige. Water (10 mL) was added and the solvent was removed under reduced pressure and replaced by ethyl acetate (10 mL). Phases decantation and extraction with ethyl acetate (2 × 7 mL) gave, after drying and evaporation, an analytically pure colorless oil which resisted to all crystallization attempts; yield: 0.93 g (93%). 1 H NMR: δ = 7.62 (d, J = 8.0 Hz, 2 H), 7.54 (d, J = 7.8 Hz, 2 H), 7.32 (t, J = 7.9 Hz, 2 H), 4.09 (d, J = 13.0 Hz, 2 H), 4.02 (d, J = 13.0 Hz, 2 H), 3.26 (s, 6 H) ppm. 13 C NMR: δ = 139.6, 138.3, 131.9, 129.9, 126.5, 124.3, 72.6, 59.0 ppm. C16H16Br2O2 (400.11) calcd. C 48.03% H 4.03% found C 47.91% H 3.91%. (-)-(P)-2,2’-Dibromo-6,6’-bis(methoxymethyl)biphenyl (P-41): Prepared following the same protocol, starting from (-)-(P)-(6,6’-dibromobiphenyl-2,2’-diyl)dimethanol (39; 1.5 g, 4.0 mmol); colorless prisms; m.p. 87 - 89 °C; [ ] 20 D α = -38.9 (c = 1.0, ethanol); yield: 1.39 g (86%).
109 (+)-(M)-2,2’-Dibromo-6,6’-bis(methoxymethyl)biphenyl (M-41): Prepared following the same protocol, starting from (+)-(M)-(6,6’-dibromobiphenyl-2,2’-diyl)dimethanol (39; 1.5 g, 4.0 mmol); colorless prisms; m.p. 86 - 88 °C; [ ] 20 α D = -37.3 (c = 1.0, ethanol); yield: 1.37 g (86%). 4.3 Preparation of Biphenylbisphosphines (-)-(P)-(6,6’-Dimethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) (42) [(-)-(P)-MeO-BIPHEP]: Butyllithium (5.4 mmol) in hexane (3.5 mL) was added dropwise to a solution of (+)-(M)- 2,2’-dibromo-6,6’-dimethoxybiphenyl (35; 1.0 g, 2.7 mmol) in toluene (8.0 mL) and diethyl ether (2.0 mL) at -75 °C. After 30 min, a solution of chlorodiphenylphosphine (1.1 mL, 1.3 g, 6.0 mmol) in toluene (10 mL) was added dropwise in order to keep the temperature below -70 °C. The mixture was then warmed up to 25 °C and water (10 mL) was added. The phases were separated and the aqueous one was extracted with ethyl acetate (2 × 10 mL) to give, after evaporation of the volatiles, a colorless solid which was recrystallized from ethanol to afford colorless needles; m.p. 213 - 215 °C (ref. [16] m.p. 214 - 215 °C); [ α ] D = -42.4 (c = 1.0, [16] chloroform), ee > 99% [ref. [ ] = -42.5 (c = 1.0, chloroform), ee 99.7%]; yield: 1.01 g 20 α (64%). D (+)-(M)-(6,6’-Dimethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) (42) [(+)-(M)-MeO-BIPHEP]: Prepared following the same protocol starting from (-)-(P)-2,2’-dibromo-6,6’- dimethoxybiphenyl (35; 1.0 g, 2.7 mmol); colorless needles; m.p. 213 - 215 °C (ref. [16] m.p. 20 D 214 - 215 °C); [ α ] = +41.7 (c = 1.0, chloroform), ee > 98.5% [ref. chloroform), ee 98.5%]; yield: 1.12 g (66%). 20 [16] 20 [ α ] D = +41.3 (c = 1.0, (±)-(PM)-(6,6’-Diethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) (43): tert-Butyllithium (30 mmol) in pentane (21 mL) was added dropwise to a solution of (±)-(PM)-2,2’-dibromo-6,6’- diethoxybiphenyl (36; 3.0 g, 7.5 mmol) in tetrahydrofuran (30 mL) at -75 °C. After 30 min, the reaction mixture was treated with a solution of chlorodiphenylphosphine (3.5 mL, 4.2 g, 19 mmol) in tetrahydrofuran (20 mL) and immediately allowed to reach 25 °C. The solvents were removed, the residue was dissolved in dichloromethane (35 mL) and water (20 mL) was added. The usual extraction procedure with dichloromethane (2 × 20 mL) afforded a white solid which was recrystallized from ethyl acetate to afford colorless prisms; m.p. 253 - 254 °C; yield: 3.89 g (85%).
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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
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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 and 128: 105 extracted with ethyl acetate (2
Page 129: 107 (+)-(M)-Dimethyl-6,6’-dibromo
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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