B. Goldfuss et al.
isopropanol. The enantiomers of the alcohols were identified by refer-
ence spectra.
ous phase was washed with diethyl ether (6 mLꢄ3) and the combined or-
ganic phases were evaporated. The remaining solid, light yellow material
was transferred into boiling n-hexanes (5 mL) and benzene was added
dropwise until the solution became homogeneous (ca. 1 mL). Crystallisa-
tion at À208C yielded 343 mg of white solid material (0.889 mmol, 42%).
M.p. 132.78C; [a]2N0a =+325 (c=1 in toluene); 1H NMR (CDCl3,
300 MHz): d=1.05 (s, 3H), 1.15 (s, 4H), 1.76 (s, 3H), 1.91 (dd, J=5.1 Hz,
1H), 2.09 (m, 2H), 5.50 (s, 1H), 7.46 (m, 7H), 7.62 (d, J=7.8 Hz, 1H),
7.78 (d, J=7.8 Hz, 1H), 7.95 (d, J=7.8 Hz, 1H), 7.99 (d, 6.9 Hz, 2H),
8.10 ppm (s, 1H); 13C NMR (CDCl3, 75.5 MHz): d=23.10, 23.40, 27.67,
34.22, 43.50, 47.10, 50.31, 79.23, 119.33, 121.72, 123.70, 127.15, 128.29,
128.43, 128.99, 133.00, 138.38, 138.63, 138.72, 145.39, 146.65, 155.71,
162.13 ppm.
Lithiation of 2,6-diphenylpyridine: 2,6-Diphenylpyridine (1 equiv,
500 mg, 2.162 mmol) were degassed in a 150 mL Schlenk tube in vacuum
for a period of 30 min. After the Schlenk was purged with argon the solid
substance was diluted in a mixture of diethyl ether (20 mL) and n-hex-
anes (20 mL). The mixture was cooled on ice bath and a 1.6m solution of
nBuLi in n-hexanes (1.2 equiv. 1.62 mL, 2.594 mmol) was added slowly
under intensive stirring. The solution was stirred for 8 h at 08C and
turned slowly to orange while yellow solid material was separated. This
crude suspension was used in the subsequent reaction without isolation
of the lithio-2,6-diphenylpyridine.
(1S,2S,4R)-1,3,3-trimethyl-2-[(R)-2-(6-phenylpyridin-2-yl)phenyl]bicyclo-
ACHTUNGTRENNUNG[2.2.1]heptan-2-ol (2): (+)-Fenchone (1.2 equiv, 0.42 mL, 2.549 mmol)
Addition of dimethylzinc to benzaldehyde:[9] Pyridylphenylene terpenol
(0.074 mmol, 5 mol%; 2: 28 mg; 6: 29 mg; 7: 28 mg) was degassed in
vacuum for a period of 10 min. The substance was dissolved in toluene
was added to the crude ice-cooled and well-stirred suspension of lithio-
2,6-diphenylpyridine. The mixture was stirred for 24 h under thawing of
the ice bath. The reaction was quenched by addition of distilled water
(10 mL) and the organic phase was separated from the water (separated
solid material was added to the organic phase). The aqueous phase was
washed diethyl ether (6 mLꢄ3) and the combined organic phases were
evaporated. The remaining solid, light yellow material was transferred
into boiling n-hexanes (5 mL) and benzene was added dropwise until the
solution became homogeneous (ca. 1 mL). Crystallisation at À208C yield-
ed 350 mg of colourless crystals (0.923 mmol, 43%). M.p. 157.88C;
[a]2N0a =À1781 (c=1 in toluene); 1H NMR (CDCl3, 300 MHz): d=0.44 (s,
3H), 0.65 (s, 3H), 1.12 (m, 1H), 1.32 (m, 2H), 1.39 (s, 3H), 1.66 (m, 2H),
2.38 (m, 1H), 2.48 (m, 1H), 6.13 (s, 1H), 7.28 (m, 3H), 7.37 (m, 1H),
7.48 (m ,3H), 7.73 (d, J=7.8 Hz, 1H), 7.85 (q, J=7.8 Hz, 2H), 8.05 ppm
(d, J=6.9 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=18.88, 21.71, 24.26,
30.40, 34.36, 41.27, 45.14, 50.70, 54.08, 86.54, 118.70, 124.81, 125.63,
126.60, 127.17, 128.85, 129.18, 133.16, 137.79, 138.42, 141.16, 144.67,
(6 mL) and
a solution of 2.0m dimethylzinc in toluene (1.8 mL,
3.6 mmol) was added at 08C. The ice bath was removed and the catalyst
was equilibrated for 30 min at room temperature. The mixture was
cooled on the ice bath again and distilled benzaldehyde (0.15 mL) was
added. The colourless solution was kept at 08C for 4 days and the reac-
tion was subsequently quenched with saturated NH4Cl solution (5 mL).
The organic phase was diluted with diethyl ether (10 mL) and rapidly
washed with 10% HCl (5 mL) and three portions a distilled water
(5 mL). The combined aqueous phases were washed with diethyl ether
(5 mLꢄ3) and the resulting combined organic phases were evaporated.
The resulting colourless oil was purified by column chromatography (n-
hexanes/ethylacetate 3:1, 70 g SiO2, Rf =0.41). The enantiomeric ratio
was determined by chiral HPLC. ((R)-1-phenylethanol: 11.2 min; (S)-1-
phenylethanol: 13.6 min).
Addition of diethylzinc to benzaldehyde:[8] Pyridylphenylene terpenol
(0.074 mmol, 5 mol%; 2: 28 mg; 6: 29 mg; 7: 28 mg) was degassed in
vacuum for a period of 10 min. The substance was dissolved in toluene
154.88, 163.94 ppm; X-ray crystal data: C27H29NO; Mr =383.51 gmolÀ1
;
space group: P212121; a=9.6472(6), b=11.3259(6), c=18.8724(8) ꢃ; V=
2062.01(2) ꢃ3; Z=4; 1=1.235 gmLÀ3; T=100(2) K; l=0.71073 ꢃ; m=
0.074 mmÀ1; total reflections: 9135; unique reflections: 2555; observed:
2072 [I>2s(I)]; parameters refined: 269; R1=0.0371, wR2=0.0774;
GOF=1.001; H atoms bound to oxygen were refined, the positions of
the H atoms bound to carbon were calculated. CCDC-773286 (2) con-
tains the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallographic
(6 mL) and
a solution of 1.0m diethylzinc in n-hexanes (2.4 mL,
2.4 mmol) was added at 08C. The ice bath was removed and the catalyst
was equilibrated for 30 min at room temperature. The mixture was
cooled on the ice bath again and distilled benzaldehyde (0.15 mL) was
added. The nearly colourless solution was kept at 08C for 4 days and the
reaction was subsequently quenched with saturated NH4Cl solution
(5 mL). The organic phase was diluted with diethyl ether (10 mL) and
rapidly washed with 10% HCl (5 mL) and three portions a distilled
water (5 mL). The combined aqueous phases were washed with diethyl
ether (5 mLꢄ3) and the resulting combined organic phases were evapo-
rated. The resulting oil was purified by column chromatography (n-hex-
anes/ethylacetate 3:1, 70 g SiO2, Rf =0,45). The enantiomeric ratio was
determined by chiral HPLC. ((R)-1-phenylpropanol: 10.2 min; (S)-1-phe-
nylethanol: 12.1 min).
(1S,2S,5R)-2-Isopropyl-5-methyl-1-[2-{(S)-6-phenylpyridin-2-yl}phenyl]-
cyclohexanol (6): (À)-Menthone (1.2 equiv, 0.45 mL, 2.549 mmol) was
added to the crude ice-cooled and well-stirred suspension of lithio-2,6-di-
phenylpyridine. The mixture was stirred for 24 h under thawing of the ice
bath and the deep orange colour turned to light yellow. The reaction was
quenched by addition of distilled water (10 mL) and the organic phase
was separated from the water. The aqueous phase was washed with dieth-
yl ether (6 mLꢄ3) and the combined organic phases were evaporated.
The remaining solid, light yellow material was transferred into boiling n-
pentane (10 mL) and benzene was added dropwise until the solution
became homogeneous. Crystallisation at À208C yielded cotton like solid
material which was washed with cold n-pentane until the light yellow
colour vanished. The organic solution still contained 6, which could be
gained by crystallisation. Yield: 293 mg (0.761 mmol, 35%); m.p.:
101.68C; [a]2N0a =+593 (c=1 in toluene); 1H NMR (CDCl3, 300 MHz):
d=0.75 (d, J=6.9 Hz, 3H), 0.78 (d, J=6.9 Hz, 3H), 0.89 (d, J=6.3 Hz,
3H), 1.56 (m, 3H), 1.81 (m, 4H), 2.23 (m, 1H), 2.97 (s, 1H), 7.28 (m,
2H), 7.44 (m, 6H), 7.72 (m, 1H), 7.85 (m, 1H), 8.02 ppm (d, J=6.6 Hz,
2H); 13C NMR (CDCl3, 75.5 MHz): d=18.79, 21.55, 22.27, 23.97, 27.34,
28.07, 35.40, 50.50, 53.18, 81.21, 117.87, 122.65, 125.74, 126.95, 127.21,
127.98, 128.63, 129.08, 132.81, 137.89 ppm.
NMR spectroscopy: Deuterated solvents were purchased from Euriso-
Top (France) ([D8]toluene) and Deutero GmbH, Kastellaun (Germany)
([D]chloroform). [D]Chloroform was dried over molecular sieves and
[D8]toluene was stored over sodium-lead alloy. NMR spectra for charac-
terisation of compounds where recorded with a Bruker DPX 300 spec-
trometer (1H frequency 300.13 MHz). 2D NMR and one-dimensional
high-resolution spectra for conformation analysis of the catalytically
active system were recorded on a Bruker AVANCE II 600 spectrometer
(1H frequency 600.20 MHz) by using a triple resonance Z gradient probe
and processed using TopSpin 2.1 software (Bruker inc.). The temperature
was calibrated with a 100% methanol sample. NMR samples were pre-
pared by dissolving degassed 2 (5 mg) in [D8]toluene (500 mL) in a
vacuum dried NMR tube to give solutions of about 0.05 molLÀ1. Dime-
thylzinc in toluene was added (0.03 mL, 56 mmol, 4.6 equiv) under argon
atmosphere in a Schlenk tube.
(1S,2S,5S)-4,6,6-Trimethyl-2-[2-{(S)-6-phenylpyridin-2-yl}phenyl]bicyclo-
Computational details: All theoretical calculations were performed with
the program package TURBOMOLE-5.10. The employed density func-
tional was BP86 with the current grid size m3 combined with the con-
tracted SVP-basis-set from Aldrich et al. The resolution of identity ap-
proximation for two-electron integral evaluation was used. All stationary
points were fully optimised and confirmed by separate analytical fre-
[3.1.1]hept-3-en-2-ol (7): (À)-Verbenone (1.2 equiv, 0.40 mL, 2.549 mmol)
was added to the crude ice-cooled and well-stirred suspension of lithio-
2,6-diphenylpyridine. The mixture was stirred for 24 h under thawing of
the ice bath. The reaction was quenched by addition of distilled water
(10 mL) and the organic phase was separated from the water. The aque-
13448
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 13443 – 13449