My PhD dissertation - Institut Fresnel

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1 H NMR (acetone-d6): δ = 7.3 (m, 11 H), 7.2 (m, 11 H), 6.79 (dd, J = 8.3, 1.0 Hz,
2 H), 6.65 (dm, 2 H), 3.72 (dq, J = 9.5, 7.0 Hz, 2 H), 3.38 (dq, J = 9.5, 7.0 Hz),
2 H), 0.92 (t, J = 6.8 Hz, 6 H) ppm.
13 C NMR (acetone-d6): δ = 135.1 (t, J = 10.5 Hz), 134.2 (t, J = 10.5 Hz), 129.2,
129.1, 129.0 (t, J = 2.8 Hz), 128.7 (m), 126.8, 112.6, 63.8, 15.1 ppm.
31 P NMR (acetone-d6): δ = - 10.8 ppm.
C40H36O2P2 (610.66) calcd. C 78.67% H 5.94%
found C 78.59% H 5.86%.
(-)-(M)-(6,6’-Diethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) (M-43): Prepared
following the same protocol starting from (+)-(M)-2,2’-Dibromo-6,6’-diethoxybiphenyl (36;
1.2 g, 3.0 mmol); colorless prisms; m.p. 211 - 213 °C; [ ] 20
α D = -39.4 (c = 0.5,
dichloromethane); ee > 98% [determined by chiral HPLC analysis on Chiracel OD-phase,
cyclohexane/ethanol (1 : 3), 1.0 ml/min]; yield: 1.52 g (83%). For crystallographic data see
Table 6, § 4.5.
(+)-(P)-(6,6’-Diethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) (P-43): Prepared
following the same protocol starting from (-)-(P)-2,2’-Dibromo-6,6’-diethoxybiphenyl (36;
1.2 g, 3.0 mmol); colorless prisms; m.p. 207 - 209 °C; [ ] 20
α D = +38.6 (c = 0.54,
dichloromethane); ee 99% [determined by chiral HPLC analysis on Chiracel OD-phase,
cyclohexane/ethanol (1 : 3), 1.0 ml/min]; yield: 1.41 g (77%).
(±)-(PM)-[6,6’-Bis(methoxymethoxy)biphenyl-2,2’-diyl]bis(diphenylphosphine) (44): To a
solution of (±)-(PM)-2,2’-dibromo-6,6’-bis(methoxymethoxy)biphenyl (34; 8.0 g, 19 mmol)
in tetrahydrofuran (0.10 L) at -75 °C, was added tert-butyllithium (76 mmol) in pentane
(52 mL) over 1 h. A solution of chlorodiphenylphosphine (8.3 mL, 9.9 g, 45 mmol) in
tetrahydrofuran (45 mL) was added dropwise so that temperature stayed below -70 °C. After
the end of addition, the mixture was allowed to reach 25 °C and water (0.10 L) was added.
Extraction with ethyl acetate (2 × 70 mL), drying with sodium sulfate and evaporation of the
volatiles gave an orange solid which was recrystallized from ethanol to afford colorless
prisms; m.p. 200 - 202 °C; yield: 10.2 g (84 %).