title: Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors.
abstract: Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C-C bonds, one C-H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti-alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotropic shift, and stereoselective protonation of the penultimate allylic organometallic intermediate. Several examples are given to demonstrate the compatibility of this reaction with substrates bearing aromatic and aliphatic substituents, and an empirical model is presented to accompany the stereochemical observations.
authors.affiliation: Department of Chemistry, Burke Laboratory, Dartmouth College , Hanover, New Hampshire 03755, United States.
authors.forename: Valer
authors.initials: V
authors.lastname: Jeso
authors.forename: Claudio
authors.initials: C
authors.lastname: Aquino
authors.forename: Xiayun
authors.initials: X
authors.lastname: Cheng
authors.forename: Haruki
authors.initials: H
authors.lastname: Mizoguchi
authors.forename: Mika
authors.initials: M
authors.lastname: Nakashige
authors.forename: Glenn C
authors.initials: GC
authors.lastname: Micalizio
mesh_terms: D000480:Alkynes / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D003500:Cyclization; D061565:Cycloaddition Reaction; D006839:Hydrocarbons, Acyclic / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D000480:Alkynes; D001643:Bridged Bicyclo Compounds; D006839:Hydrocarbons, Acyclic; D014297:Trimethylsilyl Compounds