B-allyl-10-Ph-9-borabicyclo[3.3.2]decanes: strategically designed for the asymmetric allylboration of ketones.
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 degrees C is only modestly diminished when the process is conducted at 0 degrees 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).
Canales
Eda
E
Department of Chemistry, University of Puerto Rico, Rio Piedras, PR 00931-3346.
Prasad
K Ganeshwar
KG
Soderquist
John A
JA
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001896:Boron Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis*; D008968:Molecular Conformation; D013237:Stereoisomerism
D000498:Allyl Compounds; D001896:Boron Compounds; D001643:Bridged Bicyclo Compounds; D007659:Ketones