G
P. Shaykhutdinova, M. Oestreich
Paper
Synthesis
hydrosilane (S,S)-17 was obtained as a white solid after flash column
chromatography on silica gel using cyclohexane/CH2Cl2 (10:1) as elu-
ent; mp 176–182 °C (n-pentane); Rf = 0.21 (cyclohexane/CH2Cl2 5:1).
(4S,11bS)-4-{7′-(Phenylthio)-2,2′,3,3′-tetrahydro-1,1′-spirobi[in-
den]-7-yl}-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]silepine [(S,RS)-
21]
Prepared according to GP 2 from contaminated thioether rac-20 (36
mg, mixture of the thioether and the hydrodehalogenated derivative
in a ratio of ~1:1.1) and (S)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-
e]silepine (15 mg, 0.048 mmol). The hydrosilane (S,RS)-21 (dr =
55:45) was obtained together with an unidentified silicon compound
IR (ATR, diamond): 3051 (w), 2917 (w), 2129 (w), 1583 (w), 1338 (w),
1151 (m), 811 (s), 766 (s), 744 (s), 700 cm–1 (s).
1H NMR (400 MHz, C6D6): δ = 1.94 (dd, J = 13.3, 1.5 Hz, 1 H), 2.33 (dd,
J = 2.7, 13.5 Hz, 1 H), 2.49 (dd, J = 13.5, 7.3 Hz, 1 H), 2.63 (d, J = 13.6 Hz,
1 H), 4.40–4.43 (m, 1 H), 6.83–6.89 (m, 4 H), 6.94–7.05 (m, 5 H), 7.09–
7.29 (m, 12 H),* 7.32 (d, J = 8.8 Hz, 1 H), 7.36–7.43 (m, 3 H), 7.47–7.56
(m, 5 H), 7.63–7.65 (m, 2 H), 7.69–7.75 (m, 3 H), 8.06 (d, J = 8.4 Hz, 1
H), 8.21 (d, J = 8.2 Hz, 1 H). * Signal overlapping of the C6D6 resonance
(12 H expected).
(
29Si NMR: δ = 32.0) as a white solid after flash column chromatogra-
phy on silica gel using cyclohexane/CH2Cl2 (10:1) as eluent; Rf = 0.14
(cyclohexane/CH2Cl2 5:1).
1H NMR (700 MHz, C6D6): δ = 1.99 (dd, J = 1.6, 13.4 Hz, 1 H), 2.02 (d,
J = 14.0 Hz, 1 H), 2.05–2.12 (m, 3 H), 2.18–2.22 (m, 2 H), 2.23–2.26 (m,
1 H), 2.28 (d, J = 13.2 Hz, 1 H), 2.31–2.36 (m, 2 H), 2.45–2.48 (m, 2 H),
2.51 (dd, J = 7.5, 13.2 Hz, 1 H), 2.76–2.92 (m, 10 H), 4.11–4.13 (m, 1 H),
4.33–4.34 (m, 1 H), 6.69–6.72 (m, 1 H), 6.77–6.78 (m, 1 H), 6.82 (d, J =
8.3 Hz, 1 H), 6.83–6.84 (m, 2 H), 6.86–7.01 (m, 11 H), 7.02–7.05 (m, 1
H), 7.09–7.21 (m, 11 H),* 7.24 (d, J = 8.3 Hz, 1 H), 7.27–7.29 (m, 2 H),
7.30 (d, J = 8.5 Hz, 1 H), 7.39 (mc, 2 H), 7.42–7.46 (m, 3 H), 7.60 (d, J =
8.1 Hz, 1 H), 7.66–7.68 (m, 3 H), 7.76–7.82 (m, 5 H). * Signal overlap-
ping of C6D6 resonance (11 H expected).
The following of the expected 60 13C NMR resonances were detected:
13C NMR (101 MHz, C6D6): δ = 20.4, 20.7, 125.1, 125.2, 125.9, 126.3,
126.4, 126.7, 126.7, 126.8, 126.9, 127.1, 127.4, 127.4, 127.5, 128.5,
128.6, 128.7, 129.0, 129.0, 129.2, 129.5, 130.2, 130.6, 130.6, 130.9,
130.9, 131.4, 132.1, 132.9, 133.0, 133.0, 133.1, 133.4, 133.8, 133.8,
134.6, 135.1, 136.1, 136.2, 136.4, 136.7, 140.6, 140.9, 141.2, 141.5,
144.4.
29Si DEPT NMR (99 MHz, C6D6): δ = –7.5.
HRMS (APCI): m/z [M – H]+ calcd for C60H41SSi: 821.2693; found:
The following of the expected 90 13C NMR resonances were detected:
821.2691.
13C NMR (176 MHz, C6D6): δ = 20.8, 20.8, 21.4, 22.6, 31.4, 31.4, 31.4,
31.4, 37.5, 37.5, 40.6, 40.8, 63.8, 63.8, 122.9, 123.1, 124.7, 124.8,
124.9, 126.3, 126.3, 126.4, 126.4, 126.6, 126.7, 126.8, 126.8, 126.9,
126.9, 127.0, 127.1, 127.5, 127.5, 128.5, 128.5, 128.5, 128.6, 128.7,
128.7, 128.7, 128.9, 128.9, 129.2, 129.3, 129.3, 129.4, 129.5, 131.1,
132.6, 132.7, 132.7, 132.7, 132.9, 133.0, 133.1, 133.2, 133.3, 133.3,
133.4, 133.4, 133.4, 133.5, 133.5, 133.7, 134.7, 135.2, 135.7, 136.0,
136.2, 136.8, 136.8, 136.8, 137.1, 143.5, 143.5, 145.5, 145.6, 149.3,
149.5, 156.1, 156.6.
(4S,11bS)-1,7-Diphenyl-4-{2′-(phenylthio)-5,5′,6,6′,7,7′,8,8′-octa-
hydro-[1,1′-binaphthalen]-2-yl}-4,5-dihydro-3H-dinaphtho[2,1-
c:1′,2′-e]silepine [(S,S)-18]
Prepared according to GP 2 from contaminated thioether (S)-16 (82
mg, mixture of the thioether and the hydrodehalogenated derivative
in a ratio of ~3:1) and dihydrosilane (S)-8 (56 mg, 0.121 mmol) in 10%
yield (9.5 mg, calculated with the mass of the pure thioether). The hy-
drosilane (S,S)-18 was obtained as a white solid after flash column
chromatography on silica gel (3 runs) using cyclohexane/CH2Cl2
(10:1) as eluent; mp 135–140 °C (n-pentane); Rf = 0.27 (cyclohex-
ane/CH2Cl2 5:1)
29Si DEPT NMR (99 MHz, C6D6): δ = –10.8, –11.2.
HRMS (APCI): m/z [M – H]+ calcd for C45H35SSi: 635.2223; found:
635.2229.
IR (ATR, diamond): 2919 (w), 2851 (w), 2114 (w), 1580 (w), 1338 (w),
1150 (w), 835 (m), 765 (m), 748 (m), 700 cm–1 (s).
Generation of Intramolecularly Sulfur-Stabilized Silicon Cations;
General Procedure 3 (GP 3)
1H NMR (700 MHz, C6D6): δ = 1.23–1.41 (m, 4 H),* 1.51–1.62 (m, 4 H),
2.12 (d, J = 13.2 Hz, 1 H), 2.14–2.21 (m, 2 H), 2.30–2.35 (m, 2 H), 2.41–
2.48 (m, 3 H), 2.57 (d, J = 13.7 Hz, 1 H), 2.63–2.67 (m, 3 H), 4.63–4.65
(m, 1 H), 6.74 (d, J = 8.3 Hz, 1 H), 6.89–6.93 (m, 3 H), 7.00–7.03 (m, 4
H), 7.12–7.15 (m, 3 H), 7.20–7.23 (m, 3 H), 7.24–7.27 (m, 3 H), 7.39–
7.40 (m, 2 H), 7.51 (s, 1 H), 7.53–7.54 (m, 2 H), 7.57 (d, J = 8.6 Hz, 1 H),
7.59–7.60 (m, 2 H), 7.61 (d, J = 8.6 Hz, 1 H), 7.78 (s, 1 H), 8.11 (d, J = 8.3
Hz, 1 H), 8.16 (d, J = 8.3 Hz, 1 H). * Signal overlapping of the n-pentane
and H grease resonances (4 H expected).
In a glovebox, a solution of the indicated hydrosilane (1.00 equiv) in
1,2-Cl2C6D4 (0.4 mL) was added to a solution of [Ph3C]+[B(C6F5)4]–
(1.00 equiv) in 1,2-Cl2C6D4 (0.2 mL) in an 8 mL vial. The resulting mix-
ture is transferred to a Young NMR tube, and directly subjected to
NMR spectroscopic analysis.
(4S,11bS)-1,7-Diphenyl-4-{2′-(phenylthio)-[1,1′-binaphthalen]-2-
yl}-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]silepinylium
Tetrakis(pentafluorophenyl)borate [(S,S)-6]
The following of the expected 60 13C NMR resonances were detected:
Prepared according to GP 3 from (S,S)-17 (7.8 mg, 9.4 μmol, 1.0 equiv)
and [Ph3C]+[B(C6F5)4]– (8.7 mg, 9.4 μmol, 1.0 equiv).
13C NMR (176 MHz, C6D6): δ = 20.5, 20.6, 23.0, 23.1, 23.6, 23.8, 27.6,
28.5, 29.9, 30.5, 125.1, 125.1, 126.0, 126.3, 126.3, 126.8, 126.8, 127.4,
127.4, 127.5, 128.6, 128.6, 128.6, 129.1, 129.3, 129.5, 129.7, 130.1,
130.3, 130.6, 130.7, 130.8, 131.0, 132.9, 133.0, 133.5, 133.5, 133.8,
133.9, 133.9, 134.8, 135.0, 135.4, 135.6, 136.2, 136.6, 136.7, 140.1,
140.3, 140.5, 140.9, 141.5, 141.5, 145.9.
29Si DEPT NMR (99 MHz, C6D6): δ = –7.5.
HRMS (APCI): m/z [M – H]+ calcd for C60H49SSi: 829.3319; found:
1H NMR (700 MHz, 1,2-Cl2C6D4): δ = 1.44 (d, J = 15.4 Hz, 1 H), 2.34 (d,
J = 15.4 Hz, 1 H), 3.05 (d, J = 14.5 Hz, 1 H), 3.13 (d, J = 14.5 Hz, 1 H),
6.50 (d, J = 7.5 Hz, 2 H), 6.66 (mc, 2 H), 6.76–6.79 (m, 1 H), 6.98–7.53
(m, 11 H),* 7.55–7.62 (m, 6 H), 7.65–7.71 (m, 7 H), 7.77–7.81 (m, 4 H),
7.98 (d, J = 8.4 Hz, 1 H), 8.08–8.13 (m, 3 H). * Signal overlapping of 1,2-
Cl2C6D4, benzene, Ph3CH and remaining [Ph3C]+[B(C6F5)4]– resonances
(11 H expected).
The following of the expected 84 13C NMR resonances were detected:
829.3311.
13C NMR (176 MHz, 1,2-Cl2C6D4): δ = 19.4, 20.2, 113.9, 120.3, 122.5,
124.8 (br m, ipso-C-[B(C6F5)4]–), 125.8, 126.0, 126.2, 126.7, 126.7,
126.9, 126.9, 128.0, 128.2, 128.4, 128.9, 129.0, 129.1, 129.2, 129.3,
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–I