Divalent activation in temporary phosphate tethers: highly selective cuprate displacement reactions.
Desymmetrization of a readily derived pseudo-C(2)-symmetric monocyclic phosphate via highly diastereoselective anti-S(N)2' allylic displacement reactions is reported. This method utilizes of a wide variety of zinc-derived organocuprates to afford E-1,2-syn-configured phosphate acid building blocks. Extension of this protocol to unsymmetric monocyclic phosphates exclusively yields 1,2-anti-configured products. Within this study, stereoelectronic factors, coupled with allylic strain, ultimately govern regio- and diastereoselective cuprate reactions, further substantiating the Corey mechanism for organocuprate additions into allylic esters. [reaction: see text]
Whitehead
Alan
A
Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, KS 66045-7582, USA.
McParland
James P
JP
Hanson
Paul R
PR
D000438:Alcohols / Q000138:chemical synthesis; D020650:Combinatorial Chemistry Techniques; D004952:Esters; D008958:Models, Molecular; D015394:Molecular Structure; D010755:Organophosphates / Q000737:chemistry*; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
D000438:Alcohols; D004952:Esters; D010755:Organophosphates; D015032:Zinc