Sulfoxide-controlled S(N)2' displacements between cyanocuprates and epoxy vinyl sulfoxides.
Two short and convergent routes have been devised for the preparation of enantiomerically pure acyclic epoxy vinyl sulfoxides. These substrates undergo highly regio- and stereoselective S(N)2' displacements with lithium cyanocuprates to give alpha'-alkylated, gamma-oxygenated Z alpha,beta-unsaturated sulfoxides in moderate to good yields and with good to excellent diastereoselectivities. The absolute configuration of the newly formed carbon-carbon bond is primarily controlled by the chiral sulfur atom, which in a nonreinforcing situation can override the intrinsic anti tendency of the vinyl oxirane moiety and forces the cuprate to undergo syn addition. The hydroxy vinyl sulfoxide functionality of the resulting adducts should allow for subsequent asymmetric transformations thus enhancing the synthetic usefulness of this methodology.
Marino
J P
JP
Department of Chemistry, The University of Michigan, Ann Arbor 48109-1055, USA. iqofp19@fresno.csic.es
Anna
L J
LJ
Fernández de la Pradilla
R
R
Martínez
M V
MV
Montero
C
C
Viso
A
A
D003300:Copper; D004852:Epoxy Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013450:Sulfones; D013454:Sulfoxides / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
D004852:Epoxy Compounds; D009942:Organometallic Compounds; D013450:Sulfones; D013454:Sulfoxides; D014753:Vinyl Compounds; D003300:Copper