My PhD dissertation - Institut Fresnel

More documents

Recommendations

Info

102 was added and the phases were separated. The aqueous layer was extracted with ethyl acetate (2 × 0.30 L), the combined organic phases were dried with sodium sulfate and the solvent was evaporated. The black residue was triturated with cold methanol and filtered to afford the [ ] product as colorless crystals; m.p. 215 - 217 °C (ref. 235 m.p. 215 °C); yield: 113 g (64%). 1 H NMR: δ = 7.66 (d, J = 8.0 Hz, 4 H), 7.16 (t, J = 8.0 Hz, 2 H) ppm. 13 C NMR: δ = 142.3, 132.0, 131.0, 124.7 ppm. (±)-(PM)-6,6’-Dibromobiphenyl-2,2’-diol (31): At -75 °C, butyllithium (0.14 mol) in hexane (64 mL) was added to a solution of 2,2’,6,6’-tetrabromo-1,1’-biphenyl (30; 33 g, 70 mmol) in tetrahydrofuran (0.35 L) at -75 °C. The mixture was then consecutively treated with fluorodimethoxyborane diethyl etherate [177] (39 mL, 35 g, 0.21 mol) and at 0 °C, with a 2.0 M aqueous sodium hydroxide solution (0.15 L, 0.30 mol). After 30 min, a 35% aqueous hydrogen peroxide solution (18 mL, 0.21 mol) was added and the white slurry was stirred for 1 h. Phases were decanted and extracted with ethyl acetate (2 × 0.10 L), and the combined organic layers washed with a saturated aqueous sodium sulfite solution. Drying with sodium sulfate and removal of the solvent left a dark brown paste which was precipitated in hexanes an recrystallized from toluene to afford the expected product as white prisms; m.p. 165 - 166 °C; yield: 18.2 g (76%). 1 H NMR: δ = 7.31 (dd, J = 8.2, 1.2 Hz, 2 H), 7.25 (t, J = 8.1 Hz, 2 H), 7.01 (dd, J = 8.2, 1.2 Hz, 2 H), 4.8 (s broad, 2 H) ppm. 13 C NMR: δ = 155.1, 132.0, 125.7, 125.5, 122.5, 115.2 ppm. C12H8Br2O2 (344.00) calcd. C 41.90% H 2.34% found C 41.98% H 2.30%. Optical resolution of (±)-(PM)-6,6’-Dibromobiphenyl-2,2’-diol (31): Racemic 6,6’-dibromobiphenyl-2,2’-diol (31; 15 g, 44 mmol) and (-)-(1R,2R)-1,2-diaminocyclohexane (33; 5.1 g, 44 mmol) were heated in boiling ethanol (0.10 L) for 10 min and the solution was stirred for 3 h while slowly decreasing the temperature to 25 °C. Hexanes was then added (10 mL) and the solution was kept a 5 °C for 24 h until crystallisation occurred. The solid was collected by filtration and directly recrystallized from ethanol to afford colorless prisms (6.91 g). Decomposition of the complex with 10% hydrochloric acid (30 mL) and the usual
103 extraction protocol with ethyl acetate (2 × 20 mL) afforded the enriched (P)-(-)-(3) enantiomer. This protocol was repeated until optical rotatory power remained constant; colorless prisms; m.p. 180 - 181 °C; [ ] 20 α D = -42.9 (c = 1.0, ethanol); ee > 99% [determined by conversion to (+)-MeO-BIPHEP]; yield: 5.80 g (39%). The residue obtained after evaporation of the combined mother liquor was decomposed the same way. The whole procedure was then applied to the enriched (M)-(+)-(31) enantiomer obtained, using (1S,2S)-1,2-diaminocyclohexane. Filtration of the complex and decomposition afforded colorless prisms; m.p. 178 - 180 °C; [ ] 20 α D = +42.0 (c = 1.0, ethanol); ee > 98% [determined by conversion to (-)-MeO-BIPHEP]; yield: 6.31 g (42%). C12H8Br2O2 (344.00) calcd. C 41.90% H 2.34% found C 41.84% H 2.33%. (±)-(PM)-2,2’-Dibromo-6,6’-bis(methoxymethoxy)biphenyl (34): A solution of 6,6’-dibromobiphenyl-2,2’-diol (31; 26 g, 76 mmol) in tetrahydrofuran (75 mL) was added dropwise to a 60% suspension of sodium hydride in mineral oil (6.1 g, 0.15 mol) in tetrahydrofuran (75 mL) at 25 °C. After 30 min, a solution of freshly prepared chloromethyl methyl ether (13 mL, 13 g, 0.17 mol) in tetrahydrofuran (35 mL) was added dropwise at 0 °C. After the end of addition, the reaction mixture was warmed up to 25 °C and water was added (0.10 L). Phases were decanted, the aqueous one was extracted with ethyl acetate (2 × 75 mL) and the combined organic layers were dried with sodium sulfate. After removal of the solvent, the white solid left was recrystallized from methanol to afford tiny colorless platelets; m.p. 153 - 155 °C; yield: 30.8 g (94%). 1 H NMR: δ = 7.34 (dd, J = 7.9, 1.3 Hz, 2 H), 7.22 (t, J = 8.0 Hz, 2 H), 7.17 (dd, J = 8.3, 1.3 Hz, 2 H), 5.07 (d, J = 6.7 Hz, 2 H), 5.05 (d, J = 6.7 Hz, 2 H), 3.36 (s, 6 H) ppm. 13 C NMR: δ = 157.6, 130.0, 129.1, 125.8, 124.9, 113.7, 94.5, 56.0 ppm. C16H16Br2O4 (432.10) calcd. C 44.47% H 3.73% found C 44.38% H 3.87%. (-)-(P)-2,2’-Dibromo-6,6’-bis(methoxymethoxy)biphenyl (P-34): Prepared following the same protocol, starting from (-)-(P)-6,6’-dibromobiphenyl-2,2’-diol (31); m.p. 66 - 68 °C; [ ] 20 α D = -29.7 (c = 1.03, acetone).
Page 1:
Various Facets of Organophosphorus
Page 5:
III Remerciements Je tiens à remer
Page 9:
3.3.6 Relevance of the Data Assesse
Page 13:
VII Literature References 115 Compo
Page 17:
IX Version Abrégée Les composés
Page 21 and 22:
1 Introduction 1 The present thesis
Page 23 and 24:
3 research groups in the field are
Page 25 and 26:
5 However, this mechanism suffers f
Page 27:
7 At first, a double bromine/lithiu
Page 30 and 31:
10 Although the most frequently emp
Page 32 and 33:
12 The preparation of the latter ph
Page 34 and 35:
protected to its dioxolane derivati
Page 36 and 37:
N (S)-14 1) NBS, THF, - 75 °C 2) -
Page 39 and 40:
3 Alkaline Decomposition of Phospho
Page 41 and 42:
3.2 Alkyl Carbanions Stabilities in
Page 43 and 44:
3.3.1 Mechanistic Discussion on the
Page 45 and 46:
25 The assumption reported by these
Page 47 and 48:
27 However, in the eventuality of a
Page 49 and 50:
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 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: 101 4 The Preparation and Racemate
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
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
show all

My PhD dissertation - Institut Fresnel

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?