Stereoselective reactions of acyclic allylic phosphates with organocopper reagents.
A series of acyclic allylic alcohols of general structure R(1)CH==CHCH(OH)R(2) were resolved by Sharpless kinetic resolution. The hydroxyl groups of these enantiomerically enriched alcohols were derivatized to diethyl phosphates, and the derivatives were reacted with organocopper reagents. Cleanest substitution reactions were observed with reagents R(3)(2)CuCNLi(2). With R(1) = Me and R(3) = n-Bu, the size of R(2) affected both the regioselectivity and stereoselectivity of the displacement. Larger R(2) groups gave higher regio- and stereoselectivities: with R(2) = 3-pentyl, >98% S(N)2' regioselectivity and >98% anti stereoselectivity were observed. Bn(2)CuCNLi(2) gave stereoselectivities comparable to those observed with n-Bu(2)CuCNLi(2) but t-Bu(2)CuCNLi(2) exhibited much lower diastereofacial preference.
Belelie
J L
JL
The Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
Chong
J M
JM