American Chemical Society
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B-Allyl-10-Ph-9-borabicyclo[3.3.2]decanes:  Strategically Designed for the Asymmetric Allylboration of Ketones

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journal contribution
posted on 2005-08-24, 00:00 authored by Eda Canales, K. Ganeshwar Prasad, John A. Soderquist
The simple and efficient syntheses of B-allyl-10-(phenyl)-9-borabicyclo[3.3.2]decane (1) in both enantiomeric forms are reported. The remarkable enantioselectivity (81−99% ee) of these reagents in the allylboration process at −78 °C is only modestly diminished when the process is conducted at 0 °C, a phenomenon attributable to its rigid bicyclic structure. In addition to providing the homoallylic alcohols 6 efficiently (70−92%), the procedure also permits the efficient recovery of the chiral boron moiety (67−82%) as an air-stable crystalline N-methylpseudoephedrine complex 4 for the direct regeneration of 1 with allylmagnesium bromide in ether (98%). The reagent gives predictable stereochemistry, providing a strategically designed “chiral pocket” which is particularly receptive to leading methyl groups (e.g., methyl ethyl ketone, 87% ee).