title: Redox and Lewis acid relay catalysis: a titanocene/zinc catalytic platform in the development of multicomponent coupling reactions.
abstract: A titanocene-catalyzed multicomponent coupling is described herein. Using catalytic titanocene, phosphine, and zinc dust, zinc acetylides can be generated from the corresponding iodoalkynes to affect sequential nucleophilic additions to aromatic aldehydes. The intermediate propargylic alkoxides are trapped in situ with acetic anhydride, which are susceptible to a second nucleophilic displacement upon treatment with a variety of electron-rich species, including acetylides, allyl silanes, electron-rich aromatics, silyl enol ethers, and silyl ketene acetals. Additionally, employing cyclopropane carboxaldehydes led to ring-opened products resulting from iodine incorporation. Taken together, these results form the basis for a new mode of three-component coupling reactions, which allows for rapid access to value added products in a single synthetic operation.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Joseph B
authors.initials: JB
authors.lastname: Gianino
authors.forename: Catherine A
authors.initials: CA
authors.lastname: Campos
authors.forename: Antonio J
authors.initials: AJ
authors.lastname: Lepore
authors.forename: David M
authors.initials: DM
authors.lastname: Pinkerton
authors.forename: Brandon L
authors.initials: BL
authors.lastname: Ashfeld
mesh_terms: D000089:Acetic Anhydrides / Q000737:chemistry*; D002384:Catalysis; D004987:Ethers / Q000737:chemistry*; D006847:Hydrocarbons, Iodinated / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D012821:Silanes / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D000089:Acetic Anhydrides; D004987:Ethers; D006847:Hydrocarbons, Iodinated; D058116:Lewis Acids; D009942:Organometallic Compounds; D012821:Silanes; C406884:titanocene; C031800:acetic anhydride; D015032:Zinc