Double diastereoselective intramolecular cyclopropanation to P-chiral [3.1.0]-bicyclic phosphonates.
[reaction: see text] A double diastereotopic differentiation strategy on a phosphonoacetate template is described. The approach utilizes Rh(2)(OAc)(4)-catalyzed intramolecular cyclopropanation (ICP) employing the (R)-pantolactone auxiliary in the ester functionality of the phosphonoacetate. The olefinic diastereofacial selectivity is governed by inherent electronic and steric interactions in the reacting carbene intermediate, while the group selectivity is dictated by the chiral auxiliary. This approach is being developed as an effective method to access bicyclic P-chiral phosphonates.
Moore
Joel D
JD
Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045-7582, USA.
Sprott
Kevin T
KT
Wrobleski
Aaron D
AD
Hanson
Paul R
PR
D002384:Catalysis; D018360:Crystallography, X-Ray; D003498:Cyclic P-Oxides / Q000138:chemical synthesis*; D003521:Cyclopropanes / Q000737:chemistry*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
D003498:Cyclic P-Oxides; D003521:Cyclopropanes; D007202:Indicators and Reagents