Jean-Luc Muller et al.
COMMUNICATIONS
35 bar. After the reaction, the reactor was cooled to room
temperature and worked-up as described above.
2-Phenyl-3a,4,5,6,7,7a-hexahydro-4,7-methanoinden-1-
one (9): H NMR (300 MHz, CDCl3): d=1.03 (m, 2H), 1.23
1
(m, 2H), 1.53 (m, 2H), 2.15 (m, 1H), 2.25 (m, 1H), 2.39 (m,
1H), 2.57 (m, 1H), 7.27 (m, 3H), 7.52 (d, 1H), 7.61 (m,
2H); 13C NMR (75 MHz, CDCl3): d=28.4, 29.2, 31.3, 38.4,
39.5, 47.7, 55.0, 127.1, 128.4, 131.6, 146.1, 160.3, 209.0.
2-(3-Hydroxypropyl)-3a,4,5,6,7,7a-hexahydro-4,7-meth-
Recycling Experiments
After the reaction, the reactor was cooled to room tempera-
ture and depressurised. The reaction solution was carefully
removed from the autoclave by syringe under argon. The
Raney cobalt remained in the reactor, mainly attached to
the stir bar and was washed twice with 2.5 mL THF. The
combined solutions were concentrated and analysed by GC-
MS. A new substrate/THF solution was added and the reac-
tion was repeated in the same manner.
1
anoinden-1-one (11): H NMR (300 MHz, DMSO): d=0.91
(m, 2H), 1.26 (m, 2H), 1.58 (m, 4H), 2.11 (m, 5H), 2.57 (s,
1H), 3.36 (m, 2H), 4.44 (t, 1H), 7.27 (s, 1H); 13C NMR
(75 MHz, DMSO): d=20.8, 27.8, 28.5, 30.6, 30.6, 37.4, 38.4,
47.4, 52.9, 60.2, 148.1, 159.1, 209.8; MS (CI, methane): m/z
(%)=206 (36.5%, M+), 188 (93.6%, M+ÀH2O), 173
(33.33%, M+ÀH2O2), 150 (39.7%), 145 (30.15%), 131
(21.0%, M+ÀC3H7O2), 122 (77.8%, M+ÀC5H8O), 105
(30.16%), 91 (B), 77 (58.7%), 67 (71.4%), 53 (23.8%), 41
(42.8%), 31 (22.7%).
2-Propyl-3a,4,5,6,7,7a-hexahydro-4,7-methanoinden-1-
one (13): 1H NMR (300 MHz, CDCl3): d=0.99 (m, 5H),
1.27 (m, 2H), 1.42 (m, 2H), 1.59 (m, 2H), 2.11 (m, 4H),
2.36 (m, 1H), 2.55 (m, 1H), 7.09 (s, 1H); 13C NMR
(75 MHz, CDCl3): d=13.9, 21.1, 26.7, 28.4, 29.1, 31.0, 38.0,
40.0, 48.1, 53.9, 149.2, 158.9, 211.3; MS (CI, methane): m/z
(%)=190 (B, M+); 175 (32.5%, M+ÀCH3); 162 (55%,
M+ÀCO), 161 (62.5%, M+ÀC2H5); 147 (31%, M+ÀC3H7),
124 (56%), 95 (50%, M+ÀC6H8O), 91 (67.5%), 79 (60%),
67 (31%).
2-Hexyl-3a,4,5,6,7,7a-hexahydro-4,7-methanoinden-1-
one (15): 1H NMR (300 MHz, CDCl3): d=0.92 (m, 5H),
1.19 (m, 8H), 1.36 (m, 2H), 1.52 (m, 2H), 2.05 (m, 4H),
2.30 (m, 1H), 2.49 (m, 1H), 7.03 (s, 1H); 13C NMR
(75 MHz, CDCl3): d=14.1, 22.5, 24.7, 27.8, 28.4, 29.1, 31.0,
31.6, 38.0, 39.0, 48.1, 53.9, 149.5, 158.7, 211.3; MS (CI, meth-
ane): m/z (%)=232 (M+, 34.8%), 203 (19.6%, M+ÀC2H5),
189 (12.7%, M+ÀC3H7) 175 (15.2%, M+ÀC4H5), 163 (B), 91
(34.2%), 67 (34.3%), 41 (21.0%).
PKR of Solid Phase-Bound Substrate 16
Raney cobalt (15.0 mg, 0.25 mmol) was added to a dry and
degassed window-equipped, 10-mL stainless steel autoclave
under a counter current flow of argon. The substrate-con-
tainingcarboxy-polystyrene beads (249.1 m, g loadin: g
0.25 mmol pentynol 10) were added to the reaction vessel.
A solution of norbonene 7 (282.2 mg, 2.90 mmol, 12 equivs.)
in 4.0 mL THF was added. The reactor was charged with
15 bar of CO at room temperature and heated under rigor-
ous shakingto 120 8C for 16 h. Under these reaction condi-
tions the pressure in the autoclave increased to 21 bar. After
coolingand venting, the solution was filtered and 170.1 mg
of the remainingpolymer were swollen in 2 mL dichlorome-
thane (DCM) for 10 min. Afterwards 2 mL of a solution of
TFA in DCM were added and mixed for 1 h to cleave of the
product 11. The remainingsolution was filtered and stirred
over 0.5 gK CO3 for 10 min. The cleavage procedure was
2
repeated twice with each sample to ensure quantitative re-
covery of the bound substrate/product. The combined solu-
tions were concentrated and analysed by GC with 1-decanol
as standard.
Characterisation of the Products
Diethyl 3,3a,4,5-tetrahydro-5-oxopentalene-2,2(1H)-dicar-
boxylate (2): H NMR (300 MHz, CDCl3): d=1.22 (q, 6H),
Acknowledgements
1
1.67 (t, 1H), 2.10 (m, 2H), 2.53–2.77 (m, 2H), 3.24 (q, 2H),
4.17 (m, 4H), 5.87 (s, 1H); 13C NMR (75 MHz, CDCl3): d=
13.0, 34.1, 37.9, 41.1, 44.0, 59.8, 61.1, 124.6, 170.5, 184.7,
208.7; MS (CI, methane): m/z (%)=266 (4.7%, M+), 244
(27.0%), 221 (4.7%, M+ÀC2H5O), 215 (B), 192 (8.8%,
M+ÀC2H6), 119 (20.0%, M+À147), 93 (61.2%), 65 (25.3%),
55 (24.7%).
This work was supported by the BMBF (Project Nr.
03X2007C “Nanoselox“) and the Fonds der Chemischen In-
dustrie. J. L. M. thanks Luxemburgꢀs Ministry of Culture and
Research, for awarding a research scholarship and Dr. J.
Klankermayer for helpful discussions. Furthermore we are
grateful to Prof. Eilbracht for fruitful discussions and the
group of Prof. Dr. A. Behr for the ICP measurements.
Diethyl
3,3a,4,5-tetrahydro-6-methyl-5-oxopentalene-
1
2,2(1H)-dicarboxylate (4): H NMR (300 MHz, CDCl3): d=
1.22 (q, 6H), 1.58 (m, 1H), 1.65 (s, 3H), 2.05 (d, 2H), 2.53–
2.75 (m, 2H), 3.13 (m, 2H), 4.16 (m, 4H); 13C NMR References
(75 MHz, CDCl3): d=8.5, 14.0, 34.0, 39.7, 41.39, 42.7, 61.0,
61.9, 126.1, 171.0, 177.8, 209.4; MS (CI, methane): m/z
(%)=280 (22.0%, M+), 235 (10.8%, M+ÀC2H5O), 206
(70.8%, M+ÀC4H10O), 178 (21.7%, M+ÀC5H11O2), 133 (B,
M+ÀC6H10O4), 105 (40.4%), 91 (25.0%).
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4,5,6,6a-Tetrahydro-5,5-bis(hydroxymethyl)pentalen-
2(1H)-one (6): 1H NMR (300 MHz, DMSO): d=1.02 (t,
2H), 1.93 (m, 2H), 2.47 (d, 2H), 3.28 (m, 1H), 3.42 (m,
4H), 4.63 (t, 1H), 4.74 (t, 1H), 5.79 (s, 1H); 13C NMR
(75 MHz, DMSO): d=32.8, 35.8, 42.3, 44.0, 51.4, 65.3,
123.63, 191.0, 209.7.
[4] T. Shibata, Adv. Synth. Catal. 2006, 348, 2328–2336.
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Adv. Synth. Catal. 2007, 349, 287 – 291