Reversibility effects on the stereoselectivity of Pt(II)-mediated cascade poly-ene cyclizations.
Cyclization of 1,5-dienes bearing nucleophilic traps with electrophilic trisphosphine pincer ligated Pt(II) complexes results in the formation of a polycyclic Pt-alkyl via a Pt(eta2-alkene) intermediate. With electron-rich triphosphine ligands, an equilibrium between the Pt(eta2-alkene) and Pt-alkyl was observed. The position of the equilibrium was sensitive to ligand basicity, conjugate acid strength, solvent polarity, and ring size. In cases where the ligand was electron poor and did not promote retrocyclization, the kinetic products adhering to the Stork-Eschenmoser postulate were observed (E-alkenes give trans-ring junctions). When retrocyclization was rapid, alternative thermodynamic products resulting from multistep rearrangements were observed (cis-[6,5]-bicycles). Under both kinetic and thermodynamic conditions, remote methyl substituents led to highly diastereoselective reactions. In the case of trienol substrates, long-range asymmetric induction from a C-ring substituent was considerably attenuated and only modest diastereoselectivity was observed (approximately 2:1). The data suggest that for a tricyclization, the long-range stereocontrol results from diastereo-selecting interactions that develop during the organization of the nascent rings. In contrast, the bicyclization diastereoselectivities result from reversible cascade cyclization.
Feducia
Jeremiah A
JA
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
Gagné
Michel R
MR
D000475:Alkenes / Q000737:chemistry*; D003500:Cyclization; D007700:Kinetics; D008024:Ligands; D010984:Platinum / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry; D013816:Thermodynamics
D000475:Alkenes; D008024:Ligands; D012997:Solvents; D013449:Sulfonamides; D010984:Platinum