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. 2011 Apr 15;13(8):1992-5.
doi: 10.1021/ol200392u. Epub 2011 Mar 16.

Enantioselective syntheses of syn- and anti-β-hydroxyallylsilanes via allene hydroboration-aldehyde allylboration reactions

Ming Chen  1 , William R Roush
Affiliations

Enantioselective syntheses of syn- and anti-β-hydroxyallylsilanes via allene hydroboration-aldehyde allylboration reactions

Ming Chen et al. Org Lett. .

Abstract

The kinetic hydroboration of allenylsilane 5 with ((d)Ipc)(2)BH at -40 °C provides allylborane 9Z with ≥12:1 selectivity. When the hydroboration is performed at temperatures above -40 °C, 9Z isomerizes to the thermodynamically more stable allylborane 9E with >20:1 selectivity. Subsequent treatment of 9Z or 9E with aldehydes at -78 °C provides syn- or anti-β-hydroxyallylsilanes, 7 or 8, respectively.

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Figures

Figure 1
Figure 1
Hydroboration of allenylstannane 1 and planned hydroboration of allenylsilane 2 with (dIpc)2BH.
Figure 2
Figure 2
1H NMR studies of hydroboration of allenylsilane 5 in d8-toluene. 1H resonances in the olefinic region (8–5.5 ppm) are displayed in the partial spectra.
Figure 3
Figure 3
Comparision of the hydroboration-isomerization pathways for allenylstannane 1 and allenylsilane 5.
Scheme 1
Scheme 1
Proposed Kinetic Hydroboration of 5 and Thermodynamically Controlled Allylborane Isomerization
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