title: Stereospecific Palladium-Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions.
abstract: We report the development of a Pd-catalyzed process for the cross coupling of unactivated primary, secondary, and tertiary alkylcarbastannatrane nucleophiles with acyl electrophiles. Reactions involving optically active alkylcarbastannatranes occur with exceptional stereofidelity and with net retention of absolute configuration. Because the stereochemistry of the resulting products is entirely reagent-controlled, this process may be viewed as a general, alternative approach to the preparation of products typically accessed via asymmetric enolate methodologies. Additionally, we report a new method for the preparation of optically active alkylcarbastannatranes, which should facilitate their future use in stereospecific reactions.
authors.affiliation: Department of Chemistry, The City College of New York (CCNY), 160 Convent Avenue, New York, NY, 10031, USA.|The Graduate Center of the City University of New York (CUNY), 365 Fifth Avenue, New York, NY, 10016, USA.
authors.forename: Chao-Yuan
authors.initials: CY
authors.lastname: Wang
authors.affiliation: Department of Chemistry, The City College of New York (CCNY), 160 Convent Avenue, New York, NY, 10031, USA.|The Graduate Center of the City University of New York (CUNY), 365 Fifth Avenue, New York, NY, 10016, USA.
authors.forename: Glenn
authors.initials: G
authors.lastname: Ralph
authors.affiliation: Department of Chemistry, The City College of New York (CCNY), 160 Convent Avenue, New York, NY, 10031, USA.
authors.forename: Joseph
authors.initials: J
authors.lastname: Derosa
authors.affiliation: Department of Chemistry, The City College of New York (CCNY), 160 Convent Avenue, New York, NY, 10031, USA.|The Graduate Center of the City University of New York (CUNY), 365 Fifth Avenue, New York, NY, 10016, USA.
authors.forename: Mark R
authors.initials: MR
authors.lastname: Biscoe
mesh_terms: D000215:Acylation; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D009942:Organometallic Compounds; C000628645:carbastannatrane; D010165:Palladium
keywords: carbastannatrane; cross coupling; enolate; palladium catalysis; stereospecific catalysis