Angewandte
Chemie
Clasby, D. A. Griffith, B. R. Henke, M. J. Sharp, Synlett 1995,
467 – 474; d) D. J. Denhart, D. A. Griffith, C. H. Heathcock, J.
Org. Chem. 1998, 63, 9616 – 9617.
(m, 2H), 1.75–1.16 (m, 32H), 1.05–0.85 (m, 36H) 0.66–0.53 ppm
(m, 12H); 13C NMR (125 MHz, CDCl3): d = 158.9, 151.3, 132.7,
131.9, 128.4, 113.6, 88.4, 83.8, 80.7, 79.7, 74.5, 69.4, 68.9, 63.5,
60.5, 55.4, 50.8, 44.5, 42.2, 41.1, 38.8, 38.1, 37.5, 33.8, 30.5, 29.9,
29.5, 27.7, 25.3, 25.1, 24.9, 24.4, 23.3, 23.1, 21.6, 13.9, 9.4, 7.2, 7.1,
5.5, 4.6 ppm; IR (film): n˜ = 2956, 2929, 2875, 1615, 1528, 1463,
[8] a) M. J. Sung, H. I. Lee, Y. Chong, J. K. Cha, Org. Lett. 1999, 1,
2017 – 2019; b) M. J. Sung, H. I. Lee, H. B. Lee, J. K. Cha, J. Org.
Chem. 2003, 68, 2205 – 2208; c) H. I. Lee, M. J. Sung, H. B. Lee,
J. K. Cha, Heterocycles 2004, 62, 407 – 422.
[9] S. Hourcade, A. Ferdenzi, P. Retailleau, S. Mons, C. Marazano,
Eur. J. Org. Chem. 2005, 1302 – 1310.
1254, 1094, 1032 cmÀ1
;
LRMS (ESI): m/z calcd for
C60H111N2O5Si2Sn [M+H]+: 1115.7; found: 1115.8.
[24] Attempts to achieve sequential deprotection of the primary TES
ether and oxidation by use of Swern oxidation conditions were
unsuccessful; for this procedure, see: A. Rodriguez, M. Nomen,
B. W. Spur, J. J. Godfroid, Tetrahedron Lett. 1999, 40, 5161 –
5164.
[10] a) R. Downham, F. W. Ng, L. E. Overman, J. Org. Chem. 1998,
63, 8096 – 8097; b) S. Jaroch, R. T. Matsuoka, L. E. Overman,
Tetrahedron Lett. 1999, 40, 1273 – 1276; c) C. J. Douglas, S.
Hiebert, L. E. Overman, Org. Lett. 2005, 7, 933 – 936.
[11] An intramolecular Sonogashira coupling was used in the model
studies of Heathcock and co-workers; see reference [7c].
[12] For the early use of enantiopure chiral oxazolidines in asym-
metric synthesis, see: a) D. Seebach, J. D. Aebi, Tetrahedron Lett.
1983, 24, 3311 – 3314; b) G. Calderari, D. Seebach, Helv. Chim.
Acta 1985, 68, 1592 – 1604.
[13] For a review of the chemistry of N-sulfonyliminium ions, see:
S. M. Weinreb, Top. Curr. Chem. 1997, 190, 131 – 184.
[14] For a recent review of metathesis reactions in total synthesis, see:
K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. 2005, 117,
4564 – 4601; Angew. Chem. Int. Ed. 2005, 44, 4490 – 4527.
[15] For reviews of the intramolecular Stille coupling, see: a) M. A. J.
Duncton, G. Pattenden, J. Chem. Soc. Perkin Trans. 1 1999,
1235 – 1246; b) G. Pattenden, D. J. Sinclair, J. Organomet. Chem.
2002, 653, 261– 268.
[16] The relative configuration at the aminal stereocenter was
determined by 1H–1H NOESY and ROESY spectroscopic
experiments.
[17] For a review of oxidations with IBX, see: H. Tohma, Y. Kita,
Adv. Synth. Catal. 2004, 346, 111 – 124.
[18] Grignard reagent 16 was prepared by treating the corresponding
lithium reagent with MgBr2; for the preparation of this lithium
reagent, see: D. Seyferth, S. C. Vick, J. Organomet. Chem. 1978,
144, 1 – 12.
[19] The diastereoselectivity in the addition of Grignard reagent 16 to
aldehyde 14 was approximately 3:1.
[25] K. C. Nicolaou, J. Y. Ramphal, Y. Abe, Synthesis 1989, 898 – 901.
[26] Characterization data for 27: Rf = 0.41(9:1hexanes/EtOAc
containing 2% Et3N); 1H NMR (500 MHz, CDCl3): d = 7.29 (d,
J = 8.5 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H), 6.41–6.11 (m, 4H),
5.58–5.49 (m, 1H), 5.42–5.33 (m, 1H), 4.99 (d, J = 11.5 Hz, 1H),
4.54 (d, J = 11.5 Hz, 1H), 4.29 (t, J = 8.0 Hz, 1H), 4.17–4.10 (m,
1H), 3.81 (s, 3H), 3.73 (d, J = 8.0 Hz, 1H), 3.31 (d, J = 11.7 Hz,
1H), 3.16–3.01(m, 3H), 3.00–2.85 (m, 3H), 2.84–2.71(m, 2H),
2.68–2.54 (m, 2H), 2.50–2.43 (m, 1H), 2.33–2.13 (m, 2H), 1.86–
1.78 (m, 2H), 1.77–0.80 (m, 59H), 0.66–0.49 ppm (q, J = 7.9 Hz,
6H); 13C NMR (125 MHz, CDCl3): d = 158.6, 151.4, 139.9, 132.7,
132.1, 131.8, 128.4, 125.1, 113.6, 87.7, 83.4, 82.6, 79.8, 74.6, 69.3,
68.9, 60.4, 55.5, 51.0, 44.5, 42.2, 41.1, 38.8, 38.2, 37.6, 37.0, 33.5,
29.5, 27.7, 25.3, 25.1, 25.0, 24.8, 24.4, 23.4, 23.2, 21.6, 14.0, 9.5, 7.3,
5.6 ppm; IR (film): n˜ = 2931, 2875, 1615, 1515, 1463, 1248, 1175,
1119, 1102, 1077, 1044, 1007 cmÀ1; LRMS (ESI): m/z calcd for
C58H100IN2O4SiSn [M+H]+: 1163.6; found: 1163.6.
[27] Characterization data for 28: Rf = 0.43 (3:1hexanes/EtOAc
containing 2% Et3N); 1H NMR (500 MHz, CDCl3): d = 7.30 (d,
J = 8.6 Hz, 2H), 6.91(d, J = 8.6 Hz, 2H), 6.80–6.68 (m, 1H),
6.16–6.06 (m, 2H), 5.65–5.48 (m, 3H), 4.94 (d, J = 11.5 Hz, 1H),
4.87 (d, J = 9.7 Hz, 1H), 4.64 (s, 1H), 4.52 (d, J = 11.5 Hz, 1H),
4.23–4.15 (m, 1H), 3.83 (s, 3H), 3.59–3.45 (m, 3H), 3.25–2.98 (m,
5H), 2.82–2.71 (m, 1H), 2.58–2.48 (m, 1H), 2.46–2.30 (m, 4H),
2.22–2.11 (m, 2H), 1.84–0.79 (m, 34H), 0.63 ppm (q, J = 7.7 Hz,
6H); 13C NMR (125 MHz, CDCl3): d = 159.1, 133.5, 131.9, 131.8,
128.9, 128.8, 126.6, 126.5, 113.8, 88.5, 84.4, 73.0, 72.0, 71.5, 64.5,
63.6, 61.3, 59.7, 55.5, 43.3, 43.2, 42.8, 39.5, 38.9, 29.9, 28.3, 27.1,
26.7, 26.5, 25.8, 24.4, 23.7, 23.1, 22.8, 21.8, 7.3, 5.6 ppm; IR (film):
3250 (br), 2931, 2875, 1615, 1517, 1465, 1250, 1042 cmÀ1; HRMS
(ESI): m/z calcd for C46H75N2O4Si [M+H]+: 747.5496; found:
747.5492.
[20] C. Taillier, B. Gille, V. Bellosta, J. Cossy, J. Org. Chem. 2005, 70,
2097 – 2108.
[21] Characterization data for 20: Rf = 0.24 (4:1hexanes/EtOAc
containing 2% Et3N); 1H NMR (500 MHz, CDCl3): d = 7.30 (d,
J = 8.6 Hz, 2H), 6.87 (d, J = 8.6 Hz, 2H), 4.70 (d, J = 11.1 Hz,
1H), 4.41 (d, J = 11.1 Hz, 1H), 4.19–4.15 (m, 1H), 3.92 (dd, J =
11.9, 3.3 Hz, 1H), 3.81 (s, 3H), 3.69–3.62 (m, 2H), 3.62–3.54 (m,
2H), 3.28 (s, 2H), 3.13 (d, J = 9.2 Hz, 1H), 3.10 (s, 1H), 3.08–3.02
(m, 1H), 2.76–2.66 (m, 3H), 2.64–2.58 (m, 1H), 2.13–2.08 (m,
1H), 2.08–2.00 (m, 1H), 1.96–1.92 (m, 1H), 1.75–1.66 (m, 3H),
1.60–1.10 (m, 23H), 0.88 (s, 9H), 0.03 ppm (s, 6H); 13C NMR
(125 MHz, CDCl3): d = 158.9, 131.2, 129.2, 113.7, 87.8, 85.8, 80.1,
70.5, 68.5, 65.5, 63.2, 59.1, 59.0, 55.2, 49.9, 43.8, 42.5, 41.0, 39.3,
38.6, 38.4, 33.2, 29.6, 27.7, 26.8, 26.0, 25.7, 25.2, 25.1, 24.2, 23.7,
22.4, 21.6, 18.3, À5.3 ppm; IR (film): n˜ = 3400 (br), 2928, 2854,
1613, 1514, 1471, 1388, 1361, 1302, 1248, 1097, 906 cmÀ1; HRMS
(ESI): m/z calcd for C40H69N2O5Si [M+H]+: 685.4976; found:
685.4988.
[28] Dess–Martin periodinane was prepared using the procedure of
Schreiber; see: S. D. Meyer, S. L. Schreiber, J. Org. Chem. 1994,
59, 7549 – 7552.
[29] Comparisons were made after adding CD3CO2D.[1c]
[22] For a pertinent review, see: M. T. Reetz, Acc. Chem. Res. 1993,
26, 462 – 468.
[23] Characterization data for 24: Rf = 0.62 (4:1hexanes/EtOAc
containing 2% Et3N); 1H NMR (500 MHz, CDCl3): d = 7.29 (d,
J = 8.7 Hz, 2H), 6.85 (d, J = 8.7 Hz, 2H), 6.31–6.14 (m, 2H), 4.99
(d, J = 11.5 Hz, 1H), 4.54 (d, J = 11.5 Hz, 1H), 4.30 (t, J = 6.8 Hz,
1H), 4.16–4.09 (m, 1H), 3.81 (s, 3H), 3.72 (d, J = 8.0 Hz, 1H),
3.68–3.58 (m, 2H), 3.28 (d, J = 11.7 Hz, 1H), 3.17–3.03 (m, 3H),
2.97–2.88 (m, 1H), 2.87–2.76 (m, 1H), 2.75–2.68 (m, 1H), 2.68–
2.55 (m, 2H), 2.49–2.42 (m, 1H), 2.11–1.99 (m, 2H), 1.86–1.76
Angew. Chem. Int. Ed. 2006, 45, 2912 –2915
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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