title: Catalysis and chemodivergence in the interrupted, formal homo-Nazarov cyclization using allylsilanes.
abstract: A chemodivergent, Lewis acid catalyzed allylsilane interrupted formal homo-Nazarov cyclization is disclosed. With catalytic amounts of SnCl4 and in the presence of allyltrimethylsilane, a formal Hosomi-Sakurai-type allylation of the oxyallyl cation intermediate is observed. A variety of functionalized donor-acceptor cyclopropanes and allylsilanes were shown to be amenable to the reaction transformation and the allyl products were formed in up to 92% yield. Under dilute reaction conditions with stoichiometric SnCl4 and at reduced temperatures, an unusual formal [3 + 2]-cycloaddition between the allylsilane and the oxyallyl cation occurred to give hexahydrobenzofuran products in up to 69% yield.
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.
authors.forename: Raynold
authors.initials: R
authors.lastname: Shenje
authors.forename: Corey W
authors.initials: CW
authors.lastname: Williams
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Francois
authors.forename: Stefan
authors.initials: S
authors.lastname: France
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001572:Benzofurans / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003521:Cyclopropanes / Q000737:chemistry; D015394:Molecular Structure; D012821:Silanes / Q000737:chemistry*; D017971:Tin Compounds / Q000737:chemistry*; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D000475:Alkenes; D001572:Benzofurans; D003521:Cyclopropanes; D012821:Silanes; D017971:Tin Compounds; D014297:Trimethylsilyl Compounds; C511847:allylsilane; C041694:stannic chloride; C440774:allyltrimethylsilane