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23. Regioisomeric ratio (r.r.) was determined by 1H NMR analysis of the product
mixture after flash column chromatography. Regioisomers 4 and 13 were
separable by HPLC: see Supplementary data for details.
J¼10.1 Hz, 1H), 3.77 (app. t, J¼5.4 Hz, 1H), 3.60 (d, J¼4.7 Hz, 2H),
3.48–3.45 (m, 2H), 2.86–2.78 (m, 1H), 1.89–1.82 (m, 1H), 1.76–1.69
(m, 3H), 1.57–1.46 (m, 4H), 1.36 (ddd, J¼13.2, 7.9, 4.7 Hz, 1H), 1.09–
1.04 (m, 1H), 0.95 (d, J¼7.3 Hz, 3H), 0.95 (d, J¼6.9 Hz, 3H), 0.94 (d,
J¼6.6 Hz, 3H), 0.92 (s, 9H), 0.91 (d, J¼7.3 Hz, 3H), 0.89 (d, J¼6.6 Hz,
3H), 0.11 (s, 3H), 0.08 (s, 3H); 13C NMR (126 MHz, CDCl3)
d 134.3,
131.9, 131.8, 119.0, 81.0, 80.6, 66.1, 41.3, 38.0, 37.0, 36.3, 35.3, 32.4,
32.2, 30.4, 26.1, 20.5, 18.2, 16.6, 16.2, 15.4, 4.1, ꢀ3.9, ꢀ4.1; IR (thin
film, NaCl) 3374, 2958, 2929, 2856, 1616, 1517, 1457, 1379, 1258,
1030, 836, 773 cmꢀ1; HRMS (EI, Na) calcd for C27H54O4SiNa m/z
493.36891 (MþNa); observed m/z 493.36919 (MþNa)þ.
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34. See Supplementary data for experimental details on the preparation of diene 27.
35. See Supplementary data for experimental details on the preparation of homoallylic
alcohol 28.
We gratefully acknowledge financial support of this work by the
American Cancer Society (RSG-06-117-01), the Arnold and Mabel
Beckman Foundation, Boehringer Ingelheim, Eli Lilly & Co., Bristol-
Myers Squibb (for a graduate fellowship to H.L.S.). The authors also
thank Professor Kevin Burgess for helpful discussions, Professor Ian
Paterson for providing spectral data for compound 3, and Holly
Reichard for assistance in preparing the Supplementary data sec-
tion that accompanies this manuscript.
Supplementary data
36. Takaya, H.; Ohta, T.; Inoue, S. i.; Tokunaga, M.; Masato, K.; Noyori, R. Org. Synth.
1995, 72, 74–85.
37. Perry, M. C.; Cui, X. H.; Powell, M. T.; Hou, D. R.; Reibenspies, J. H.; Burgess, K.
J. Am. Chem. Soc. 2003, 125, 113–123.
38. Zhou, J. G.; Burgess, K. Angew. Chem., Int. Ed. 2007, 46, 1129–1131.
39. Diastereoselectivity could not be determined due to overlapping peaks in the
crude 1H NMR spectrum.
Complete experimental details for all preparative procedures
along with spectral data for all products are provided. Supple-
mentary data associated with this article can be found in the online
40. Diastereomer 18 was separable by HPLC: see Supplementary data for details.
41. As the chiral iridium catalyst does not require a coordinating functional group,
we also examined the hydrogenation with the protected homoallylic ether 38.
Although 38 was completely consumed upon exposure to D-34 (725 psi H2,
CH2Cl2, 3 h), significant amounts of products resulting from PMP deprotection
and low levels of diastereoselectivity (ca. 1.3:1) were observed.
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