title: Stereoretentive Pd-catalysed Stille cross-coupling reactions of secondary alkyl azastannatranes and aryl halides.
abstract: The development of transition metal-catalysed cross-coupling reactions has greatly influenced the manner in which the synthesis of complex organic molecules is approached. A wide variety of methods are now available for the formation of C(sp(2))-C(sp(2)) bonds, and more recent work has focused on the use of C(sp(3)) electrophiles and nucleophiles. The use of secondary and tertiary alkyl nucleophiles in cross-coupling reactions remains a challenge because of the propensity of these alkyl groups to isomerize under the reaction conditions. Here, we report the development of a general Pd-catalysed process for the stereoretentive cross-coupling of secondary alkyl azastannatrane nucleophiles with aryl chlorides, bromides, iodides and triflates. Coupling partners with a wide range of electronic characteristics are well tolerated. The reaction occurs with minimal isomerization of the secondary alkyltin nucleophile, and with retention of absolute configuration. This process constitutes the first general method to use secondary alkyltin reagents in cross-coupling reactions.
authors.affiliation: Department of Chemistry, The City College of New York, 160 Convent Avenue, New York, New York 10031, USA.
authors.forename: Ling
authors.initials: L
authors.lastname: Li
authors.forename: Chao-Yuan
authors.initials: CY
authors.lastname: Wang
authors.forename: Rongcai
authors.initials: R
authors.lastname: Huang
authors.forename: Mark R
authors.initials: MR
authors.lastname: Biscoe
mesh_terms: D002384:Catalysis; D006219:Halogens / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D017971:Tin Compounds / Q000737:chemistry*
chemical_list: D006219:Halogens; D017971:Tin Compounds; D010165:Palladium