366
R. Fürst et al.
PAPER
IR (ATR): 3460, 2932, 2359, 2341, 1512, 1459, 1363, 1301, 1245,
1172, 1147, 1092, 1031, 914 cm–1.
Supporting Information for this article is available online at
rimental procedures and analytical data of all intermediates, descri-
bed within this manuscript, can be found in the supporting
information.SnoIufrpmootgiraitnSugioIormaoptritnf
1H NMR (400 MHz, CDCl3): δ = 0.93 (d, J = 6.6 Hz, 3 H), 1.07 (d,
J = 6.8 Hz, 3 H), 1.22–1.31 (m, 1 H), 1.52 (ddd, J = 4.3, 10.5, 13.8
Hz, 1 H), 2.08–2.16 (m, 1 H), 2.43–2.56 (m, 1 H), 3.18 (dd, J = 3.9,
5.9 Hz, 1 H), 3.23 (d, J = 3.9 Hz, 1 H), 3.27–3.31 (m, 2 H), 3.42 (s,
3 H), 3.62–3.69 (m, 1 H), 3.80 (s, 3 H), 4.44 (s, 2 H), 4.67 (d, J = 6.8
Hz, 1 H), 4.76 (d, J = 6.8 Hz, 1 H), 4.99–5.02 (m, 1 H), 5.02–5.06
(m, 1 H), 5.76–5.88 (m, 1 H), 6.84–6.90 (m, 2 H), 7.22–7.28 (m, 2
H).
13C NMR (100 MHz, CDCl3): δ = 16.9 (CH3), 17.7 (CH3), 30.4
(CH), 37.9 (CH2), 40.0 (CH), 55.4 (CH3), 56.2 (CH3), 69.8 (CH),
72.6 (CH2), 76.3 (CH2), 88.7 (CH), 98.9 (CH2), 113.6 (CH), 115.3
(CH2), 129.3 (CH), 130.8 (C), 139.9 (CH), 159.2 (C).
References
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HRMS (ESI): m/z [M + Na]+ calcd for C20H32O5: 375.2148; found:
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(4R,5S)-3-((S)-3-{(4R,5R)-5-[(R)-2-(tert-Butyldimethylsil-
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(59)
A 0.1 M solution of SmI2 in THF (31.3 mL, 3.13 mmol, 2.5 equiv)
was transferred into a 250-mL round bottom Schlenk flask which
was precooled to –78 °C. A solution of bromide 20 (449 mg, 1.38
mmol, 1.1 equiv) and aldehyde 58 (390 mg, 1.25 mmol, 1.0 equiv)
in degassed THF (20 mL, 3 pump-freeze-thaw cycles) was added to
the SmI2 solution via a cannula over a period of 5 min. The mixture
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of aq sat. Na2S2O3 (20 mL) and aq sat. NaHCO3 (20 mL) at –78 °C.
The biphasic system was allowed to warm to r.t. The two phases
were separated, and the aqueous layer was extracted with EtOAc
(3 × 30 mL). The combined organic extracts were dried (Na2SO4),
filtered, and the organic solvents were removed under reduced pres-
sure delivering the crude secondary alcohol as a light yellow oil that
was purified by flash chromatography (hexane–EtOAc, 9:1) provid-
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[α]D20 +34.4 (c 1.0, CHCl3).
IR (ATR): 3511, 3264, 2933, 2858, 2361, 2341, 1773, 1688, 1457,
1338, 1248, 1151, 1086, 1028, 987, 835, 768 cm–1.
1H NMR (400 MHz, CDCl3): δ = 0.23 (s, 3 H), 0.30 (s, 3 H), 0.90
(s, 9 H), 0.91 (d, J = 6.6 Hz, 3 H), 1.36 (s, 3 H), 1.44 (s, 3 H), 1.48
(s, 3 H), 1.58 (s, 3 H), 1.71 (s, 3 H), 2.58 (s, 1 H), 3.32 (d, J = 4.8
Hz, 1 H), 4.08 (d, J = 6.3 Hz, 1 H), 4.27 (d, J = 6.3 Hz, 1 H), 4.81
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7.31 (m, 2 H), 7.33–7.44 (m, 3 H).
13C NMR (100 MHz, CDCl3): δ = –2.9 (CH3), –2.2 (CH3), 14.4
(CH3), 18.5 (C), 20.2 (CH3), 22.4 (CH3), 25.7 (CH3), 26.1 (CH3),
26.4 (CH3), 28.2 (CH3), 50.6 (C), 57.7 (CH3), 69.1 (CH), 69.5 (C),
74.0 (CH), 75.7 (CH), 79.2 (CH), 84.5 (CH), 86.9 (C), 108.5 (C),
125.8 (CH), 128.8 (CH), 128.9 (CH), 133.8 (C), 152.6 (C), 177.0
(C).
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using the major S-configured alcohol.
HRMS (ESI): m/z [M + Na]+ calcd for C30H45NO7Si: 582.2863;
found: 582.2859 +/– 5.
Acknowledgment
R.F. is a recipient of a DOC-fFORTE-fellowship of the Austrian
Academy of Sciences at the Department of Organic Chemistry,
University of Vienna. The authors thank the NMR department at the
University of Vienna for assistance. The Fonds zur Förderung der
wissenschaftlichen Forschung (Austrian Science Fund, FWF) is
gratefully acknowledged for financial support of this work (Project
Number FWF-P20697-N19).
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Synthesis 2014, 46, 357–367
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