10642
F. Alonso et al. / Tetrahedron 65 (2009) 10637–10643
m/z 158 (Mþ, 1%), 115 (17), 113 (41), 101 (30), 88 (100), 85 (11), 73
(22), 70 (20), 61 (17), 60 (25), 55 (19).
1.89 [13H, m, (CH2)5, CH2CH3, NH], 2.37–2.44 (1H, m, CH), 2.58 (2H, t,
J¼7.3, CH2N); dC 11.8 (CH3), 23.4, 25.0, 26.1, 33.6, 48.8 (7ꢃCH2), 56.8
(CH); m/z 141 (Mþ, 19%), 112 (47), 98 (100), 70 (12), 56 (25), 55 (14).
4.2.5. Ethyl hexanoate (Table 3, entry 3). Colourless oil; tr 6.24; Rf
0.15 (hexane/EtOAc 95:5); dH 0.89(3H, t, J¼6.8, CH2CH2CH3),1.22–1.36
[7H, m, (CH2)2CH3, OCH2CH3], 1.59–1.65 (2H, m, CH2CH2CO), 2.23–
2.31 (2H, m, CH2CO), 4.12 (2H, q, J¼7.1, OCH2CH3); dC 14.1 (2ꢃCH3),
22.2, 24.6, 31.2, 34.6, 60.0 (5ꢃCH2), 173.8 (CO); m/z 144 (Mþ, 1%), 101
(27), 99(56), 88(100), 73 (27), 71(25), 70 (29), 61 (19), 60(34), 55(23).
4.2.14. 1,2-Bis(3,4,5-trimethoxyphenyl)ethane (brittonin A)24. White
solid; mp 142–143 ꢀC (hexane); tr 19.68; Rf 0.53 (hexane/EtOAc
7:3); dH 2.85 (4H, s, 2ꢃCH2), 3.83 (18H, s, 6ꢃCH3), 6.36 (4H, s,
4ꢃArH); dC 38.4 (2ꢃCH2), 56.0 (6ꢃCH3), 105.3 (4ꢃArCH), 136.1
(2ꢃArC), 137.3, 153.0 (6ꢃArCO); m/z 362 (Mþ, 32%), 181 (100).
4.2.6. 2-Methoxy-4-(n-propyl)phenol (Table 3, entry 4). Colourless
oil; tr 10.40; Rf 0.12 (hexane/EtOAc 95:5); dH 0.92 (3H, t, J¼7.3, CH3),
1.54–1.64 (2H, m, CH2CH3), 2.49 (2H, t, J¼7.8, ArCH2), 3.80 (3H, s,
CH3O), 5.01 (1H, s, OH), 6.63 (1H, s, ArH), 6.65, 6.80 (2H, 2d, J¼8.0,
2ꢃArH); dC 13.7 (CH3), 24.5, 37.4 (2ꢃCH2), 55.4 (CH3O), 114.1, 120.6,
125.3 (3ꢃArCH), 134.3, 143.2, 146.3 (3ꢃArC); m/z 166 (Mþ, 23%), 137
(100), 122 (10).
Acknowledgements
This work was generously supported by the Spanish Ministerio
´
de Educacion y Ciencia (MEC; grant no. CTQ2007-65218; Consolider
Ingenio 2010-CSD2007-00006) and the Generalitat Valenciana
(PROMETEO2009/039). P. R. also thanks the MEC for a predoctoral
grant.
4.2.7. 4-Ethyl-1,2-dimethoxybenzene (Table 3, entry 5). Colourless
oil; tr 9.94; Rf 0.28 (hexane/EtOAc 9:1); dH 1.22 (3H, t, J¼7.5, CH3),
2.59 (2H, q, J¼7.5, CH2), 3.83, 3.86 (6H, 2s, 2ꢃCH3O), 6.71–6.72 (2H,
m, 2ꢃArH), 6.72–6.79 (1H, m, ArH); dC 15.6 (CH3), 28.2 (CH2), 55.5,
55.7 (2ꢃCH3O), 110.8, 111.0, 119.2 (3ꢃArCH), 136.7 (ArC), 146.8,
148.6 (2ꢃArCO); m/z 166 (Mþ, 61%), 164 (10), 152 (10), 151 (100), 95
(14), 91 (18), 79 (10), 77 (17).
References and notes
1. For reviews and monographs, see: (a) Takaya, H.; Noyori, R. In Comprehensive
Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 8,
Chapter 3.1; (b) Chaloner, P. A.; Esteruelas, M. A.; Jo´ o, F.; Oro, L. A. Homogeneous
Hydrogenation; Kluwer Academic: Dordrecht, 1994; (c) Cui, X.; Burguess, K.
Chem. Rev. 2005, 105, 3272–3296; (d) Catalysts for Fine Chemical Synthesis;
Roberts, S., Whittall, J., Eds.; John Wiley & Sons: New York, NY, 2007; Vol. 5,
Chapter 2; (e) Handbook of Homogeneous Hydrogenation; de Vries, J. G., Elsevier,
C. J., Eds.; Wiley-VCH: Weinheim, 2007; (f) Genet, J.-P. In Modern Reduction
Methods; Andersson, P. G., Munslow, I. J., Eds.; Wiley-VCH: Weinheim, 2008,
Chapter 1; (g) Diesen, J. S.; Andersson, P. G. In Modern Reduction Methods;
Andersson, P. G., Munslow, I. J., Eds.; Wiley-VCH: Weinheim, 2008, Chapter 2.
2. For reviews, see: (a) Siegel, S. In Comprehensive Organic Synthesis; Trost, B. M.,
Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 8, Chapter 3.2; (b) Nishimura, S.
Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis; John
Wiley & Sons: New York, NY, 2001; (c) Molnar, A.; Sarkany, A.; Varga, M. J. Mol.
Catal. A: Chem. 2001, 173, 185–221.
4.2.8. 5-Propylbenzo[d][1,3]dioxole (dihydrosafrole) (Table 3, entry
6). Yellow oil; tr 9.75; Rf 0.40 (hexane/EtOAc 95:5); dH 0.92 (3H, t,
J¼7.4, CH3), 1.56 (2H, sextet, J¼7.4, CH2CH3), 2.49 (2H, t, J¼7.4,
ArCH2), 5.87 (2H, s, CH2O), 6.58–6.72 (3H, m, 3ꢃArH); dC 13.5 (CH3),
24.7, 37.6, 100.5 (3ꢃCH2), 107.9, 108.8, 121.0 (3ꢃArCH), 136.4 (ArC),
145.3, 147.4 (2ꢃArCO); m/z 164 (Mþ, 28%), 135 (100), 77 (17).
4.2.9. Decan-3-ol (Table 3, entry 7). Colourless oil; tr 8.64; Rf 0.42
(hexane/EtOAc 9:1); dH 0.86–0.96 (6H, m, 2ꢃCH3), 1.03–1.55 (14H,
m, 7ꢃCH2), 2.37 (1H, s, OH), 3.51 (1H, quintet, J¼4.6, CH); dC 7.8, 14.1
(2ꢃCH3), 22.6, 23.9, 29.6, 30.0, 31.3, 31.8, 36.9 (7ꢃCH2), 73.2 (CH);
m/z 140 (Mþ–18, 21%), 129 (23), 111 (20), 97 (12), 84 (11), 83 (15), 70
(32), 69 (100), 67 (14), 59 (92), 58 (12), 57 (38), 56 (42), 55 (78), 54
(10), 53 (11).
3. For a review, see: Pasto, D. J. In Comprehensive Organic Synthesis; Trost, B. M.,
Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 8, Chapter 3.3.
4. For reviews, see: (a) Johnstone, R. A. W.; Wilby, A. H. Chem. Rev. 1985, 85, 129–
170; (b) Kellogg, R. M. In Comprehensive Organic Synthesis; Trost, B. M., Fleming,
I., Eds.; Pergamon: Oxford, 1991; Vol. 8, Chapter 1.3; (c) Ba¨ckvall, J.-E. J. Orga-
nomet. Chem. 2002, 652, 105–111.
5. Kitamura, M.; Noyori, R. In Ruthenium in Organic Synthesis; Murahashi, S.-I., Ed.;
Wiley-VCH: Weinheim, 2004; pp 31–32.
6. (a) Elamin, B.; Park, J. W.; Means, G. E. Tetrahedron Lett. 1988, 29, 5599–5600;
(b) Basu, B.; Das, S.; Das, P.; Nanda, A. K. Tetrahedron Lett. 2005, 46, 8591–8593;
(c) Brunel, J. M. Tetrahedron 2007, 63, 3899–3906; (d) Quinn, J. F.; Razzano, D. A.;
Golden, K. C.; Gregg, B. T. Tetrahedron Lett. 2008, 49, 6137–6140.
7. (a) Spogliarich, R.; Tencich, A.; Kaspar, J.; Graziani, M. J. Organomet. Chem. 1982,
240, 453–459; (b) Gnanamgari, D.; Moores, A.; Rajaseelan, E.; Crabtree, R. H.
Organometallics 2007, 26, 1226–1230.
8. Dhakshinamoorthy, A.; Pitchumani, K. Tetrahedron Lett. 2008, 49, 1818–1823.
9. Andrews, M. J.; Pillai, C. N. Indian J. Chem. 1978, 16B, 465–468.
10. Boldrini, G. P.; Savoia, D.; Tagliavini, E.; Trombini, C.; Umani-Ronchi, A. J. Org.
Chem. 1985, 50, 3082–3086.
11. For reviews, see: (a) Alonso, F.; Radivoy, G.; Yus, M. Russ. Chem. Bull., Int. Ed.
2003, 52, 2563–2576; (b) Alonso, F.; Yus, M. Chem. Soc. Rev. 2004, 33, 284–293;
(c) Alonso, F.; Yus, M. Pure Appl. Chem. 2008, 80, 1005–1012.
12. (a) Alonso, F.; Yus, M. Tetrahedron Lett. 1996, 37, 6925–6928; (b) Alonso, F.;
Yus, M. J. Chem. Educ. 2001, 78, 1517–1518.
13. (a) Alonso, F.; Yus, M. Adv. Synth. Catal. 2001, 343, 188–191; (b) Alonso, F.;
Candela, P.; Go´mez, C.; Yus, M. Adv. Synth. Catal. 2003, 345, 275–279.
14. (a) Alonso, F.; Osante, I.; Yus, M. Adv. Synth. Catal. 2006, 348, 305–308; (b)
Alonso, F.; Osante, I.; Yus, M. Synlett 2006, 3017–3020; (c) Alonso, F.; Osante, I.;
Yus, M. Tetrahedron 2007, 63, 93–102.
15. (a) Alonso, F.; Calvino, J. J.; Osante, I.; Yus, M. Chem. Lett. 2005, 34, 1262–
1263; (b) Alonso, F.; Calvino, J. J.; Osante, I.; Yus, M. J. Exp. Nanosci. 2006, 1,
419–433.
16. (a) Alonso, F.; Riente, P.; Yus, M. Synlett 2007,1877–1880; (b) Alonso, F.; Riente, P.;
Yus, M. Eur. J. Org. Chem. 2008, 4908–4914; (c) Alonso, F.; Riente, P.; Yus, M.
Tetrahedron 2008, 64, 1847–1852; (d) Alonso, F.; Riente, P.; Yus, M. Tetrahedron
Lett. 2008, 49, 1939–1942; (e) Alonso, F.; Riente, P.; Yus, M. Synlett 2008,
1289–1292.
4.2.10. 2-Methyl-1-phenylpropan-1-ol (Table 3, entry 8). Colourless
oil; tr 8.84; Rf 0.16 (hexane/EtOAc 9:1); dH 0.76, 0.97 (6H, 2d, J¼6.7,
2ꢃCH3), 1.85–1.94 [1H, m, CH(CH3)2], 2.0 (1H, s, OH), 4.28 (1H, d,
J¼6.1, CHO), 7.23–7.32 (5H, m, 5ꢃArH); dC 18.1, 18.8 (2ꢃCH3), 35.1,
80.0 (2ꢃCH),126.4, 127.1, 128.0 (5ꢃArCH), 143.6 (ArC); m/z 150 (Mþ,
3%),132 (67),131 (16),118 (11), 117 (100),116 (15),115 (53),107 (42),
105 (53), 91 (43), 79 (26), 78 (11), 77 (24), 65 (14), 63 (12), 51 (17).
4.2.11. 3,7-Dimethyloctan-3-ol (Table 3, entry 9). Colourless oil; tr
7.53; Rf 0.19 (hexane/EtOAc 9:1); dH 0.87–0.90 (9H, m, 3ꢃCH3), 1.16–
1.31 [7H, m, CH3C, CH2CH2CH(CH3)2], 1.32–1.58 [5H, m,
CH2C(OH)CH2, CH(CH3)2], 2.04 (1H, s, OH); dC 8.1 (CH3), 21.5 (CH2),
22.5, 26.3 (3ꢃCH3), 27.9 (CH), 34.1, 39.5, 41.5 (3ꢃCH2), 72.8 (C); m/z
140 (Mþ–18, 31%), 111 (16), 84 (10), 83 (21), 73 (38), 71 (15), 70 (88),
69 (69), 67 (19), 57 (15), 56 (31), 55 (100), 53 (17).
4.2.12. Benzyl n-propyl ether (Table 3, entry 10). Colourless oil; tr
8.20; Rf 0.14 (hexane/EtOAc 95:5); dH 0.93 (3H, t, J¼7.5, CH3), 1.58–
1.65 (2H, m, CH2CH3), 3.42 (2H, t, J¼7.3, CH2CH2CH3), 4.49 (2H, s,
ArCH2), 7.24–7.26 (5H, m, 5ꢃArH); dC 10.3 (CH3), 22.7, 70.9, 71.9
(3ꢃCH2), 127.4, 127.5, 128.1, 128.2 (5ꢃArCH), 138.3 (ArC); m/z 150
(Mþ, 2%), 92 (70), 91 (100), 79 (11), 77 (11), 65 (14).
17. The complete characterisation of the NiNPs has been recently submitted to an
specialised catalysis journal.
18. For reviews, see: (a) van der Drift, R. C.; Bouwman, E.; Drent, E. J. Orga-
nomet. Chem. 2002, 650, 1–24; (b) Uma, R.; Cre´visy, C.; Gre´e, R. Chem. Rev.
2003, 103, 27–51; (c) Cadierno, V.; Crochet, P.; Gimeno, J. Synlett 2008,
1105–1124.
4.2.13. N-(n-Propyl)cyclohexanamine (Table 3, entry 11). Yellow oil;
tr 7.40; Rf 0.25 (hexane/EtOAc 9:1); dH 0.92 (3H, t, J¼7.3, CH3), 1.01–