Ru Phosphinesulfonate for Hydrogenation of Aryl Ketones
FULL PAPER
acid (0.58 g, 3.66 mmol, 1.0 equiv) in THF (10 mL) was added nBuLi
(1.6m solution in n-hexane, 5.0 mL, 8.04 mmol, 2.2 equiv) dropwise at
08C over 10 min under an argon atmosphere. The mixture was stirred at
08C for 10 min, at RT for 10 min, at 508C for 10 min, and at RT for
10 min. Then the resulted salt was cooled at À788C. Simultaneously,
(11bS)-4-chloro-4,5-dihydro-3H-dinaphtho[2,1-c:1’,2’-e]phosphepine
(1.25 g, 3.66 mmol, 1.0 equiv) was dissolved in THF (5 mL) and cooled to
À788C. Then, the lithiated benzenesulfonic acid was transferred dropwise
through a cannula into the solution of the phosphine precursor in THF at
À788C. The reaction mixture was stirred for 1 h at À788C and allowed to
warm at RT for a further 24 h. Upon warming, the slurry became a red
solution, which turned dark red and, finally, a dark-orange, clear solution.
Evaporation of the solvent under vacuum was followed by dissolution of
the residue with degassed deionized water (10 mL) at 08C. The aqueous
layer was acidified with 1m HCl aqueous solution to pHꢀ2 at 08C and
extracted with CH2Cl2 (3ꢅ50 mL). The combined organic layers were
dried over MgSO4, filtered, and evaporated under vacuum to generate a
yellow solid. The solid was washed with distilled THF, filtered, and
washed with a minimum amount of THF to afford a white powder
(0.41 g, 23%). [a]2D0 =À191 (c=0.36, CH2Cl2); 1H NMR (400 MHz,
CD2Cl2): d=8.17 (dd, J=7.6, 4.4 Hz, 1H), 8.12 (d, J=8.4 Hz, 1H), 8.04
(d, J=8.2 Hz, 1H), 7.99 (d, J=8.1 Hz, 1H), 7.95 (d, J=8.5 Hz, 1H), 7.77
(m, 1H), 7.71 ppm (d, J=8.4 Hz, 1H), d=7.57 (m, 2H), 7.45–7.41 ppm
(m, 1H), d=7.36–7.31 (m, 3H), 7.26–7.16 (m, 3H), 4.26 (t, 1H), 3.80–
3.71 (m, 2H), 3.59–3.51 ppm (m, 1H); 13C NMR (100 MHz, CD2Cl2): d=
126.12 (signals from 131.19–126.12 all corresponded to tertiary carbon
atoms, but they were not fully characterized owing to complex P,C cou-
pling), 96.53 (Cquat), 90.08 (CH), 86.41 (d, J
(CH), 74.07 (CH), 33.88 (d, J(P,C)=20.7 Hz; CH2), 31.51(CH), 30.00 (d,
(P,C)=33.4 Hz; CH2), 22.91(CH3), 20.84(CH3), 18.55 ppm (CH3);
ACHTUNGERTN(NUNG P,C)=9.5 Hz; CH), 84.35
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31P NMR (162 MHz, CD2Cl2): d=42.34 ppm; HRMS (ESI): m/z calcd for
C38H34O3PSRu: 703.10043 [MÀCl]+; found: 703.1006.
CCDC 927220 (I) contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
quest/cif.
Acknowledgements
The authors thank the European Union (FP-7 integrated project SYN-
FLOW, NMP-2009-3.2-1, No. 246461) for financial support and for a PhD
fellowship to F.J. M.A. thanks the CNRS for a delegation. We also thank
Dr. T. Roisnel and Dr. V. Dorcet (UMR 6226: Institut des Sciences Chi-
miques de Rennes) for performing the X-ray analysis.
[1] L. G. Rao, V. T. Mathad, Chim. Oggi 2012, 30, 44.
151.19 (d, J
(d, J(P,C)=4.0 Hz; Cquat), 134.93 (d, J
(P,C)=3.2 Hz; Cquat), 134.22 (d, J(P,C)=3.2 Hz; Cquat), 132.91 (CH), 132.8
(CH), 132.48 (d, J(P,C)=2.4 Hz; Cquat), 132.31 (d, J(P,C)=3.2 Hz; Cquat),
130.79 (d, J(P,C)=2.4 Hz; CH), 130.30 (d, J(P,C)=2.38 Hz; CH), 130.21
(CH), 130.08 (CH), 128.98 (CH), 128.90 (CH), 128.22 (d, J(P,C)=4.0 Hz;
A
ACHTUNGERTN(NUNG P,C)=3.2 Hz; CH), 135.11
[2] a) J. G. de Vries, The Handbook of Homogeneous Hydrogenation,
Wiley-VCH, Weinheim, 2007; b) P. G. Andersson, I. J. Munslow,
Modern Reduction Methods, Wiley-VCH, Weinheim, 2008.
[3] a) H. U. Blaser, E. Schmidt, Asymmetric Catalysis on Industrial
Scale, Wiley-VCH, Weinheim, 2003; b) D. J. Ager, A. H. M. de V-
A
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CH), 127.52, 127.47, 127.41, 127.23, 127.17, 127.05 (signals from 127.52–
127.05 all corresponded to tertiary carbon atoms, but they were not fully
characterized owing to complex P,C coupling), 126.58 (d,
11.1 Hz; Cquat), 126.12 (d, (P,C)=8.7 Hz; Cquat), 112.76 (d,
78.7 Hz; Cquat), 28.06 (d, J
J
J
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(P,C)=54.0 Hz; CH2), 24.95 ppm (d, J
G
[5] a) T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am.
Ohkuma, K. Murata, T. Yokozawa, M. Kozawa, E. Katayama, A. F.
Pham, K. Mikami, T. Korenaga, M. Terada, R. Noyori, J. Am.
T. Pham, M. Kozawa, K. Murata, E. Katayama, T. Yokozawa, T.
Ohkuma, M. Koizumi, H. Ikehira, T. Yokozawa, R. Noyori, Org.
2001, 20, 379; b) C. Hedberg, K. Kꢆllstrçm, P. I. Arvidsson, P.
[7] a) K. Abdur-Rashid, S. E. Clapham, A. Hadzovic, J. N. Harvey, A. J.
[8] a) C. P. Casey, S. W. Singer, D. R. Powell, R. K. Hayashi, M. Kavana,
van Boxtel, L. Lefort, A. J. Minnaard, B. L. Feringa, J. G. de Vries,
47.7 Hz; CH2); 31P (162 MHz, CD2Cl2): d=15.98 ppm; HRMS (ESI): m/z
calcd for C28H21O3NaPS: 491.08467 [M+Na]+; found: 491.0849; m/z calcd
for C28H22O3PS: 469.10273 [M+H]+; found: 469.1033.
Synthesis of complex I, [Ru(h6-p-cymene)(k2-o-
ACTHUNTGRNENUG ACHTUNTGNER{NUGN (11bS)-3H-dinaph-
tho(2,1-c:1’,2’-e)phosphepin-4(5H)-yl}C6H4SO3)Cl]: 2-((11bS)-3H-Dinaph-
tho[2,1-c:1’,2’-e]phosphepin-4(5H)-yl)benzenesulfonic acid (0.792 mmol,
1.0 equiv) and tBuOK (0.871 mmol, 1.2 equiv) were added into a 25 mL
Schlenk tube. The sealed Schlenk tube was evacuated and filled with
argon three times. A minimum amount of MeOH (degassed by nitrogen
purge for 30 min) was added and the solution was stirred at RT for
30 min. To this solution was added [{Ru(h6-p-cymene)Cl2}2] (0.200 g,
0.396 mmol, 0.5 equiv). The red solution became a slurry after 1 h. After
stirring for 16 h at RT, the solution was concentrated, the MeOH was re-
moved by cannula, and the solid was washed with MeOH (2ꢅ1 mL).
Then, the crude was washed with CH2Cl2 (2ꢅ8 mL). The solution was fil-
tered through dry celite (distilled and degassed CH2Cl2) to remove the
inorganic salts. Then, the solvent was removed under vacuum to generate
complex I as an orange solid (0.37 g, 36%). [a]2D0 =À127 (c=0.1733,
CH2Cl2); 1H NMR (400 MHz, CD2Cl2): d=8.11 (d, J=8.3 Hz, 1H), 8.07
(d, J=8.3 Hz, 1H), 7.98 (ddd, J=7.6, 3.9, 1.0 Hz, 1H), 7.93 (d, J=8.0 Hz,
1H), 7.70 (d, J=8.4 Hz, 1H), 7.59–7.55 (m, 2H), 7.51–7.46 (m, 2H),
7.38–7.30 (m, 2H), 7.30–7.26 (m, 1H), 7.18–7.12 (m, 2H), 6.73 (d, J=
8.2 Hz, 1H), 6.63 (dd, J=7.9, 7.9 Hz, 1H), 5.89 (d, J=5.9 Hz, 1H), 5.54
(d, J=6.0 Hz, 1H), 4.88 (d, J=5.8 Hz, 1H), 4.71–4.68 (m, 1H), 4.17 (dd,
J=13.8, 5.6 Hz, 1H), 3.76 (dd, J=13.2, 4.1 Hz, 1H), 3.66 (m, 2H), 3.03
(qq, J=6.9, 7.0 Hz, 1H), 2.10 (s, 3H), 1.37 (d, J=7.0 Hz, 3H), 1.36 ppm
(d, J=6.8 Hz, 3H); 13C NMR (100 MHz, CD2Cl2): d=147.53 (d, J
11.1 Hz; Cquat), 135.76 (d, (P,C)=4.0 Hz; Cquat), 133.84 (d,
3.2 Hz; Cquat), 133.53 (d, J(P,C)=2.4 Hz; Cquat), 133.37 (d, J(P,C)=1.6 Hz;
quat), 132.88 (d, J(P,C)=1.6 Hz; Cquat), 132.70 (d, J(P,C)=11.9 Hz; Cquat),
132.33 (d, J(P,C)=1.6 Hz; Cquat), 132.09 (CH), 131.54 (d, J(P,C)=4.8 Hz;
ACHTUNGTRENNUNG
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Cquat), 131.19, 131.18, 129.74, 129.68, 128.96, 128.87, 128.65, 128.62,
128.45, 128.43, 128.00, 127.93, 127.47, 127.19, 126.99, 126.76, 126.62,
Chem. Eur. J. 2013, 19, 10343 – 10352
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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