title: Design, Synthesis, and Validation of an Effective, Reusable Silicon-Based Transfer Agent for Room-Temperature Pd-Catalyzed Cross-Coupling Reactions of Aryl and Heteroaryl Chlorides with Readily Available Aryl Lithium Reagents.
abstract: A reusable silicon-based transfer agent (1) has been designed, synthesized, and validated for effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent (1) is easily prepared via a one-step protocol. Importantly, this "green" CCR protocol circumvents prefunctionalization, isolation of organometallic cross-coupling partners, and/or stoichiometric waste aside from LiCl. DFT calculations support a σ-bond metathesis mechanism during transmetalation and lead to insights on the importance of the CF3 groups.
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
authors.forename: Dionicio
authors.initials: D
authors.lastname: Martinez-Solorio
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
authors.forename: Bruno
authors.initials: B
authors.lastname: Melillo
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
authors.forename: Luis
authors.initials: L
authors.lastname: Sanchez
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
authors.forename: Yong
authors.initials: Y
authors.lastname: Liang
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
authors.forename: Erwin
authors.initials: E
authors.lastname: Lam
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
authors.forename: Amos B
authors.initials: AB
authors.lastname: Smith
mesh_terms: D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D007202:Indicators and Reagents / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D013696:Temperature
chemical_list: D002712:Chlorides; D007202:Indicators and Reagents; D010165:Palladium; D008094:Lithium; D012825:Silicon
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