Organic & Biomolecular Chemistry
Page 4 of 5
COMMUNICATION
Organic & Biomolecular Chemistry
1H NMR (400 MHz, CDCl3) δ = 4.20-4.12 (m, 4H), 2.21-2.11 (m, 4H),
1.71-1.62 (m, 4H), 1.23 (t,
= 7.1 Hz, 6H); 13C NMR (101 MHz, CDCl3)
δ = 172.7, 61.1, 60.4, 34.4, 25.4, 14.0.
Chem. A, 2013, 1, 15039; d) M. E. Vol’pin, V. P. Kukolev, V. O.
Chernyshev and I. S. Kolomnikov, Tetrahedron Lett., 1971, 12, 4435; e)
J
1-(2,6,6-Trimethylcyclohex-1-en-1-yl)butan-1-one (2h). Spectrally pure
product was synthesized according to procedure A using commercially
available substrate 1h without further purification (161 mg, 83%).
Analyses were in accordance with previously reported.19
DOI: 10.1039/C4OB02480J
Russ. Chem. Bull., Int. Ed., 1971, 21, 661; f) I. S. Kolomnikov, Y. D.
Koreshkov, V. P. Kukolev, V. A. Mosin and M. E. Vol’pin, Russ. Chem.
Bull., Int. Ed., 1973, 22, 180; g) V. Jurčík ,S. P. Nolan and C. S. J. Cazin,
Chem. Eur. J., 2009, 15, 2509; h) K. Ohkubo, T. Aoji, K. Hirata and K.
Yoshinga, Inorg. Nucl. Chem. Letters, 1976, 12, 837; S. Horn and M.
Albrecht, Chem. Commun., 2011, 47, 8802; B. Schmidt, S. Krehl, V.
Sotelo-Meza, Synthesis, 2012, 1603; i) M. Lamani, G. S. Ravikumara and
K. R. Prabhu, Adv. Synth. Catal., 2012, 354, 1437; j) W. Leitner, J. M.
Brown and H. Brunner, J. Am. Chem. Soc., 1993, 115, 152; k) C. E.
Hartmann, V. Jurčík, O. Songis and C. S. J. Cazin, Chem. Commun.,
2013, 49, 1005; l) C. Menozzi, P. I. Dalko, J. Cossy, Synlett, 2005, 2449.
a) Handbook of Metathesis, eds.: R. H. Grubbs, Wiley-VCH, Weinheim,
2003; b) Olefin Metathesis Theory and Practice eds.: K. Grela, John
Wiley & Sons, Inc.: Hoboken, NY, 2014.
For reviews, see: a) D. E. Fogg and E. N. dos Santos, Coord. Chem. Rev.,
2004, 248, 2365; b) B. Schmidt and S. Krehl, Domino and Other Olefin
Metathesis Sequences In Olefin Metathesis Theory and Practice, eds.: K.
Grela, John Wiley & Sons, Inc.: Hoboken, NY, 2014 pp. 187-232.
Selected examples: a) J. Louie, C. W. Bielawski and R. H. Grubbs, J.
Am. Chem. Soc., 2001, 123, 11312; b) J. Cossy, F. C. Bargigga and S.
BouzBouz, Tetrahedron Lett., 2002, 43, 6715; c) B. Schmidt and M.
Pohler, Org. Biomol. Chem., 2003, 1, 2512; d) X. Miao, C. Fischmeister,
C. Bruneau, P. H. Dixneuf, J.-L. Dubois and J.-L. Couturier,
ChemSusChem, 2012, 5, 1410.
1H NMR (400 MHz, CDCl3) δ = 2.50 (t,
J
= 7.4 Hz, 2H), 1.93 (t,
Hz, 2H), 1.69-1.59 (m, 4H), 1.53 (s, 3H), 1.45-1.39 (m, 2H), 1.04 (s, 6H),
0.93 (t,
= 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ = 212.0, 143.6,
128.7, 47.8, 39.0, 33.3, 31.2, 28.8, 20.95, 19.0, 16.7, 13.9.
J = 6.3
J
Procedure B. Tandem Olefin Metathesis and C-C Double Bond
Reduction. Diene (1 mmol) and in 5 mL of dry THF were placed in a
reaction tube. Catalyst Gru-II (2 mol%) was added and the ring closing
metathesis reaction was carried out for 0.5 h at 40 °C. Once the RCM
reaction was completed according to TLC or GC, solid HCOONa (0.2
mmol) was added immediately followed by 98% HCOOH (50 mmol) and
the reaction was continued for appropriate period of time at 80 °C in a
closed tube, then allowed to reach room temperature and poured into
saturated aqueous solution of NaHCO3 (ca. 30 mL). The aqueous layer
was extracted with an appropriate organic solvent and the combined
organic phases were washed with brine, dried over MgSO4, filtered and
the solvent was evaporated in vacuo to obtain the crude product., which
was further purified when necessary by column chromatography or by
bulb-to-bulb distillation.
3
4
5
Diethyl cyclopentane-1,1-dicarboxylate (2a). Product was synthesized
according to procedure B using diene 1a as a starting material and NaH
instead of HCO2Na. Spectrally pure product was isolated by extraction
(214 mg, 99%). Analyses were in accordance with previously reported.18
1H NMR (400 MHz, CDCl3) δ = 4.20-4.12 (m, 4H), 2.21-2.11 (m, 4H),
6
7
T. Connolly, Z. Wang, M. A. Walker, I. M. McDonald and K. M. Peese,
Org. Lett., 2014, 16, 4444.
T. Wdowik, C. Samojłowicz, M. Jawiczuk, M. Malińska, K. Woźniak
and K. Grela, Chem. Commun., 2013, 49, 674.
1.71-1.62 (m, 4H), 1.23 (t, J
= 7.1 Hz, 6H); 13C NMR (101 MHz, CDCl3)
δ = 172.7, 61.1, 60.4, 34.4, 25.4, 14.0.
Benzoylcyclopentane (2c). Product was synthesized according to general
procedure B using diene 1c as a starting material. Purification by using
column chromatography afforded spectrally pure product 2c (160 mg,
92%). Analyses were in accordance with previously reported.20
1H NMR (400 MHz, CDCl3) δ = 8.03-7.93 (m, 2H), 7.60-7.50 (m, 1H),
8
9
T. Wdowik, C. Samojłowicz and K. Grela, unpublished results.
a) Formic acid is considered as viable and renewable feedstock for
hydrogen. Ru(II) promoted catalitic formic acid dehydrogenation to
gaseous mixture of H2 and CO2 was reported: I. Mellone, M. Peruzzini,
L. Rosi, D. Mellmann, H. Junge, M. Beller and L. Gonsalvi, Dalton
Trans., 2013, 42, 2495; b) In an open flask, the same catalytic system (2
mol% Gru-II, 50 equiv. HCOOH and 0.2 equiv. of NaH) leads to
formation of 2a in 90% yield, however, after prolonged time of 15 hours.
For detailed experimental procedures see Electronic Supporting
Information (ESI)
7.50-7.42 (m, 2H), 3.72 (quint,
J = 7.88 Hz, 1H), 2.06-1.85 (m, 4H),
1.83-1.54 (m, 4H); 13C NMR (100 MHz, CDCl3) δ = 202.9, 137.0, 132.8,
128.6, 128.6, 46.5, 30.1, 26.4.
Acknowledgements
The authors are grateful to the National Science Centre (Poland) for
the NCN Opus Grant No. UMO-2013/09/B/ST5/03535.
10 For representative examples of Ru-catalyzed transfer hydrogenation of
ketones, see: a) C. S. Cho, B. T. Kim, T.-J. Kim and S. C. Shim, J. Org.
Chem., 2001, 66, 9020; b) M. Babin, R. Clément, J. Gagnon and F-G.
Fontaine, New J. Chem., 2012, 36, 1548; c) O. O. Kovalenko, H.
Lundberg, D. Hübner and H. Adolfsson, Eur. J. Org. Chem., 2014, 6639
and Ref. 13a
Notes and references
a G. K. Zieliński, C. Samojłowicz, T. Wdowik, K. Grela
Institute of Organic Chemistry, Polish Academy of Sciences
Kasprzaka 44/52, PO Box 58, 01-224, Warsaw, Poland.
E-mail: karol.grela@gmail.com;
Fax: +48-22-632-66-81
11 Interestingly, trisubstituted alkenes were reported to be inert to Ru-
catalysed transfer hydrogenation, cf. Ref. 6
12 a) P. v. R. Schleyer, J. E. Williams and K. R. Blanchard, J. Am. Chem.
Soc., 1970, 92, 2377; b) The relative ratio of reduction with diimide is
15.5 for cyclopentene, 1.0 for cyclohexene, 12.1 for cycloheptene and
17.0 for cyclooctene, while for 1-methylcyclohexene is only 0.11. See: c)
E. W. Garbish, Jr, S. M. Schildcrout, D. B. Patterson and C. M. Sprecher,
J. Am. Chem. Soc., 1965, 87, 2932.
†
Electronic Supplementary Information (ESI) available: Full
experimental details and characterization data, including NMR spectra.
See DOI: 10.1039/c000000x/
13 a) N. Manashe, E. Salant and Y. Shvo, J. Organomet. Chem., 1996, 514,
97.; b) T. Koike and T. Ikariya, Adv. Synth. Catal., 2004, 346, 37.
14 a) B. Schmidt, Eur. J. Org. Chem., 2004, 1865; b) B. Alcaide, P.
Almendros and A. Luna, Chem. Rev., 2009, 109, 3817.
15. It cannot be excluded that both, the initial ruthenium metathesis catalyst,
and its decomposition products after olefin metathesis step, are able to
catalyse the hydrogen transfer reaction.
16. a) T. M. Trnka, J. P. Morgan, M. S. Sanford, T. E. Wilhelm, M. Scholl,
T.-L. Choi, S. Ding, M. W. Day and R. H. Grubbs, J. Am. Soc. Chem.,
2003, 125, 2546; b) M. B. Dinger and J. C. Mol, Eur. J. Inorg. Chem.
2003, 2827; d) D. Pingen, M. Lutz and D. Vogt, Organometallics, 2014,
33, 1623.
1
a) Handbook of Homogeneous Hydrogenation, eds.: J. G. de Vries and C.
J. Elsevier, Wiley-VCH, Weinheim, 2007; b) S. Siegel, Heterogeneous
Catalytic Hydrogenation of C=C and C≡C In Comprehensive Organic
Synthesis, Vol. 8 Reduction eds.: B. M. Trost, I. Fleming, Pergamon
Press, Oxford, 1993, pp. 417-443; c) H. Takaya, Homogeneous Catalytic
Hydrogenation of C=C and C≡C In Comprehensive Organic Synthesis
Vol. 8 Reduction eds.: B. M. Trost, I. Fleming, Pergamon Press, Oxford,
1993, pp. 443-471.
2
a) J. A. Osborn, F. H. Jardine, J. F. Young and G. Wilkinson, J. Chem.
Soc. A, 1966, 1711; b) R. Crabtree, Acc. Chem. Res., 1979, 12, 331. c) Q.
Zhao, Y. Li, R. Liu, A. Chen, G. Zhang, F. Zhang and X. Fan, J. Mater.
4 | Org. Biomol. Chem., 2014, 00, 1-3
This journal is © The Royal Society of Chemistry 2012