J. M. Cuerva, A. M. Echavarren et al.
1.68 (s, 6H), 1.60 (s, 3H), 1.54–1.44 (m, 2H), 1.10 (s, 3H), 1.03–0.97 ppm
(d, J=6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3, 258C): d=139.5 (CH),
134.3 (C), 130.5 (C), 124.3 (CH), 123.3 (CH), 114.8 (CH2), 72.7 (C), 46.3
(CH), 38.6 (CH2), 30.9 (CH2), 25.6 (CH2), 24.7 (CH3), 22.6 (CH3), 20.8
(CH2), 16.7 (CH3), 15.0 (CH3), 13.9 ppm (CH3).
1.85–1.78 (m, 1H), 1.81 (s, 3H), 1.73 (dt, J=13.4, 3.5 Hz, 1H), 1.64–1.55
(m, 1H), 1.17 ppm (s, 3H); 13C NMR (125 MHz, CDCl3, 258C): d=172.6
(C), 171.2 (C), 144.8 (C), 114.8 (CH2), 71.6 (C), 55.30 (C), 52.9 (CH3),
52.7 (CH3), 50.8 (CH), 38.2 (CH2), 33.4 (CH2), 29.0 (CH2), 23.01 (CH3),
22.0 ppm (CH3); HRMS (EI): m/z calcd for C14H22O5Na [M+Na]+:
293.1365; found: 293.1374.
Compound 37: Following GP 4, compound 37 was obtained as colourless
oil. 1H NMR (400 MHz, CDCl3, 258C): d=5.60 (m, 1H), 5.17 (d, J=
10.2 Hz, 1H), 5.08 (d, J=17.0 Hz, 1H), 2.06–2.05 (m, 1H), 1.51–1.16 (m,
26H), 1.07 (s, 3H), 0.87 ppm (t, J=6.3 Hz, 6H); 13C NMR (100 MHz,
CDCl3, 258C): d=139.1 (CH), 118.4 (CH2), 73.4 (C), 54.2 (CH), 39.8
(CH2), 31.9 (2ꢅCH2), 30.3 (CH2), 30.2 (CH2), 29.6 (CH2), 29.5 (CH2),
29.3 (2ꢅCH2), 28.9 (CH2), 28.1 (CH2), 28.0 (CH2), 24.2 (CH3), 23.1
(CH2), 22.6 (CH2), 14.1 ppm (2ꢅCH3); HRMS (EI): m/z calcd for
C20H40ONa [M+Na]+: 319.2977; found: 319.2979.
Compound 53: Following GP 5, compound 53 was obtained as a colour-
less oil. 1H NMR major isomer (500 MHz, CDCl3, 258C): d=5.68 (ddd,
J=17.2, 10.4, 2.2 Hz, 1H), 5.07 (d, J=8.8 Hz, 1H), 5.05 (d, J=1.2 Hz,
1H), 3.74 (s, 3H), 3.72 (s, 3H), 2.66–2.55 (m, 2H), 2.45 (d, J=14.3 Hz,
1H), 2.34 (d, J=14.3 Hz, 1H), 2.17–2.13 (m, 2H), 1.43 ppm (s, 3H);
13C NMR major isomer (100 MHz, CDCl3, 258C): d=173.5 (C), 168.5
(C), 136.8 (CH), 118.7 (CH2), 91.1 (C), 57.1 (C), 52.7 (CH3), 49.8 (CH3),
48.1 (CH), 45.1 (CH2), 34.4 (CH2), 17.3 ppm (CH3); 1H NMR minor
isomer (500 MHz, CDCl3, 258C): d=5.72 (ddd, J=17.2, 10.4, 2.2 Hz,
1H), 5.07 (d, J=8.8 Hz, 1H), 5.05 (d, J=1.2 Hz, 1H), 3.74 (s, 3H), 3.72
(s, 3H), 2.66–2.55 (m, 2H), 2.45 (d, J=14.3 Hz, 1H), 2.34 (d, J=14.3 Hz,
1H), 2.17–2.13 (m, 2H), 1.44 ppm (s, 3H); 13C NMR minor isomer
(100 MHz, CDCl3, 258C): d=173.3 (C), 168.3 (C), 135.1 (CH), 119.1
(CH2), 90.3 (C), 57.8 (C), 52.7 (CH3), 49.9 (CH3), 48.1 (CH), 45.1 (CH2),
34.1 (CH2), 16.9 ppm (CH3); HRMS (EI): m/z calcd for C12H18O5Na
[M+Na]+: 265.1052; found: 265.1060.
Compound 38: Following GP 4, compound 38 was obtained as a colour-
less oil. 1H NMR (400 MHz, CDCl3, 258C): d=5.70–5.47 (m, 1H), 5.16
(d, J=10.2 Hz, 1H), 5.07 (d, J=17.1 Hz, 1H), 2.02–1.94 (m, 1H), 1.64–
1.11 (m, 22H), 1.06 (s, 3H), 0.86 ppm (t, J=6.3 Hz, 6H); 13C NMR
(100 MHz, CDCl3, 258C): d=139.1 (CH), 118.4 (CH2), 73.4 (C), 54.2
(CH), 39.8 (CH2), 31.8 (2ꢅCH2), 30.3 (CH2), 29.6 (CH2), 29.3 (CH2), 28.9
(CH2), 27.7 (CH2), 24.2 (CH3), 23.13 (CH2), 23.09 (CH2), 22.7 (CH2), 22.6
(CH2), 14.1 (CH3), 14.0 ppm (CH3); HRMS (EI): m/z calcd for
C18H36ONa [M+Na]+: 291.2664; found: 291.2676.
Compound 54: Following GP 5, compound 54 was obtained as a colour-
less oil. 1H NMR (400 MHz, CDCl3, 258C): d=7.43–7.28 (m, 5H), 5.74
(dt, J=18.0, 9.1 Hz, 1H), 5.10 (d, J=10.2 Hz, 1H), 4.96 (d, J=17.0 Hz,
1H), 3.85 (s, 6H), 3.21–3.14 (m, 1H), 2.79–2.70 (m, 1H), 2.66 (d, J=
11.0 Hz, 1H), 2.58 (d, J=10.6 Hz, 1H), 2.08 ppm (ddd, J=13.4, 4.5,
2.3 Hz, 1H); 13C NMR (100 MHz, CDCl3, 258C): d=167.8 (C), 163.3
(C), 130.1 (C), 129.2 (CH), 123.7 (2ꢅCH), 120.4 (2ꢅCH), 123.4 (CH),
114.3 (CH2), 87.8 (C), 53.1 (C), 48.0 (2ꢅCH3), 46.1 (CH), 43.8 (CH2),
29.2 ppm (CH2); HRMS (EI): m/z calcd for C17H20O5Na [M+Na]+:
327.1208; found: 327.1210.
Compound 43: Following GP 4, compound 43 was obtained as a colour-
less oil. 1H NMR (500 MHz, CDCl3, 258C): d=5.80 (ddd, J=17.5, 10.8,
2.5 Hz, 1H), 5.13–4.98 (m, 3H), 3.36 (brs, 1H, one isomer), 3.32 (brs,
1H, other isomer), 2.09–1.88 (m, 2H), 1.67 (s, 3H), 1.60 (m, 3H), 1.52–
1.36 (m, 2H), 1.33–1.24 (m, 1H), 1.21–1.11 (m, 2H), 0.97 (d, J=6.2 Hz,
6H), 0.93 (d, J=6.7 Hz, 3H, one isomer), 0.88 ppm (d, J=6.6 Hz, 3H,
other isomer); 13C NMR (125 MHz, CDCl3, 258C): d=145.5 (CH), 124.9
(C), 124.8 (CH), 113.1 (CH2), 76.0 (CH), 75.6 (CH), 41.6 (C), 39.0 (CH2),
38.7 (CH2), 38.33 (CH2), 35.7 (CH2), 29.8 (CH) 29.2 (CH), 25.6 (2ꢅCH3),
25.2 (CH2), 23.0 (CH3), 22.0 (CH3), 20.8 (CH3), 18.8 (CH3), 17.6 ppm
(CH3); HRMS (FAB): m/z calcd for C15H28ONa [M+Na]+: 247.2037;
found: 247.2029.
Compound 44: Following GP 4, compound 44 was obtained as a colour-
less oil. 1H NMR (500 MHz, CDCl3, 258C): d=6.08 (dd, J=17.6,
10.8 Hz, 1H), 5.03–4.93 (m, 2H), 4.12 (brs, 1H), 2.03–1.95 (m, 2H), 1.77
(s, 3H), 1.63–1.42 (m, 2H), 1.42–1.31 (m, 2H), 1.11 (s, 6H), 1.07 ppm (s,
6H); 13C NMR (100 MHz, CDCl3, 258C): d=147.8 (CH), 138.6 (C),
133.8 (C), 111.0 (CH2), 77.6 (CH), 42.8 (CH2), 40.6 (C), 34.8 (CH2), 29.8
(C), 28.0 (4ꢅCH3), 25.3 (CH), 19.2 ppm (CH2); HRMS (EI) m/z calcd
for C15H26O [MÀOH]+: 205.1956; found: 205.1958.
Acknowledgements
We thank the MICINN (CTQ2007–60745/BQU, Consolider Ingenio 2010
and Grant CSD2006–0003), the AGAUR (2009 SGR 47), the ICIQ Foun-
dation and Junta de Andalucꢀa (Project P09-FQM-4571) for financial sup-
port. A.M. and A.G.C. thank MICINN for their FPU fellowships and
L.A.dC. thanks UGR for his research contract.
Compound 45: Following GP 4, compound 45 was obtained as a colour-
less oil. 1H NMR (400 MHz, CDCl3, 258C): d=5.74–5.63 (m, 1H), 5.13
(dd, J=10.9, 1.3 Hz, 1H), 5.06–5.01 (m, 1H), 5.01–4.95 (m, 1H), 3.19 (m,
1H), 1.89–1.69 (m, 2H), 1.60 (s, 3H), 1.51 (s, 3H), 1.43–1.08 (m, 18H),
0.88 (s, 3H), 0.81 ppm (t, J=6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3,
258C): d=144.3 (CH), 131.2 (C), 124.8 (CH), 115.0 (CH2), 77.1 (CH),
45.0 (C), 37.4 (CH2), 31.9 (CH2), 30.9 (CH2), 29.8 (CH2), 29.7 (CH2), 29.6
(CH2), 29.3 (CH2), 27.1 (CH2), 25.6 (CH3), 22.8 (CH2), 22.7 (CH2), 17.5
(CH3), 16.6 (CH3), 14.1 ppm (CH3); HRMS (ESI+): m/z calcd for
C20H39O [M+H]+: 295.3001; found: 295.3000.
1316; c) B. W. Gung, Org. React. 2004, 64, 1–112; d) Z. Lu, S. Ma,
[2] P. Barbier, C. R. Hebd. Seances Acad. Sci. 1899, 128, 110.
[4] Zn and B: a) J. P. Takahara, Y. Masuyama, Y. Kurusu, J. Am. Chem.
[5] Pd and Sn: a) Y. Masuyama, N. Kinugawa, Y. Kurusu, J. Org. Chem.
Commun. 1989, 356–357.
Compound 51: Following GP 5, compound 51 was obtained as a colour-
less oil. 1H NMR (500 MHz, CDCl3, 258C): d=8.09 (d, J=7.5 Hz, 2H),
8.00 (d, J=7.6 Hz, 2H), 7.76–7.63 (m, 2H), 7.58 (dt, J=17.3, 7.8 Hz,
4H), 5.86–5.65 (m, 1H), 5.15 (t, J=14.4 Hz, 1H), 3.01 (ddd, J=12.6, 8.5,
4.0 Hz, 1H), 2.69–2.58 (m, 1H), 2.27 (tdd, J=8.5, 6.9, 2.4 Hz, 1H), 2.11–
1.99 (m, 1H), 1.72–1.62 (m, 1H), 1.54 (ddd, J=14.7, 7.3, 3.4 Hz, 1H),
0.89 ppm (t, J=7.6 Hz, 3H); 13C NMR (125 MHz, CDCl3, 258C): d=
137.0 (CH), 136.7 (C), 136.2 (C), 134.4 (CH), 134.3 (CH), 131.5 (CH),
131.1(CH), 131.1 (CH), 128.6 (CH), 118.0 (CH2), 87.7 (C), 70.8 (C) , 43.6
(CH), 33.7 (CH2), 30.9 (CH2), 27.4 (CH2), 22.2 (CH2), 7.50 ppm (CH3);
HRMS (EI): m/z calcd for C22H26O5S2Na [M+Na]+: 457.1119; found:
457.1126.
[8] The group of Krische reported new allylations that use iridium com-
plexes and a source of hydrogen but the procedure seems to be lim-
ited to simple allyl and a-methyl allyl acetate as pro-nucleophiles
and aldehydes as electrophiles: a) I. S. Kim, M.-Y. Ngai, M. J. Kri-
Compound 52: Following GP 5, compound 52 was obtained as a colour-
1
less oil. H NMR (500 MHz, CDCl3, 258C): d=5.01 (s, 1H), 4.79 (s, 1H),
3.76 (s, 3H), 3.71 (s, 3H), 2.42–2.22 (m, 3H), 1.88 (t, J=13.6 Hz, 1H),
3992
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Chem. Eur. J. 2011, 17, 3985 – 3994