title: Synthesis of the purported ent-pochonin J structure featuring a stereoselective oxocarbenium allylation.
abstract: The synthesis of the alleged natural product pochonin J is presented. Key steps of this convergent synthesis include a chemoselective Wacker oxidation, and an Evans' anti-reduction of the resulting ketone. Upon ozonolysis, this intermediate undergoes a 6-exo-trig cyclization to give a hemiketal intermediate, the key oxocarbenium precursor. The construction of the α-C-glycoside subunit is highlighted by a mismatched oxocarbenium cation formation/allylation sequence. An olefin metathesis afforded the 14-membered macrolactone, and final oxidation provided the "desired" compound that does not spectroscopically correlate to the initially described natural product.
authors.affiliation: Department of Chemistry, The University of Alabama, 250 Hackberry Lane, Tuscaloosa, Alabama 35487-0336, United States.
authors.forename: Dionicio
authors.initials: D
authors.lastname: Martinez-Solorio
authors.forename: Kenneth A
authors.initials: KA
authors.lastname: Belmore
authors.forename: Michael P
authors.initials: MP
authors.lastname: Jennings
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry; D007700:Kinetics; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000475:Alkenes; D001688:Biological Products; D018942:Macrolides; C560829:ent-pochonin J